Liquid crystal alignment film and method for producing the same, and liquid crystal display apparatus using the same and method for producing the same

ABSTRACT

A positive resist mainly composed of a novolak resin and comprising a naphthoquinone diazido-based photosensitizer as an energy beam sensitive resin (e.g., a photosensitive resin) is applied in a thickness of 0.1 to 0.2 μm to a surface of a glass substrate  1  provided with transparent electrodes and dried so as to form a photosensitive film. Next, using a mask, the film is exposed to ultraviolet rays (365 nm). Then, moisture in the air reacts with the resist in an exposed portion  2 ′, thereby generating —COOH groups, with which CH 3 (CH 2 ) 18 SiCl 3  is allowed to react so as to cause a dehydrochlorination reaction, thereby forming a monomolecular chemisorption film  6  comprising carbon chains  8 . This film is used as an alignment film. Thus, the present invention provides a method for producing a uniform and thin alignment film for use in a liquid crystal display panel with a high efficiency without performing a rubbing treatment, and a method for producing a display panel using the same.

TECHNICAL FIELD

[0001] The present invention relates to an image display apparatusemploying liquid crystal and a method for producing such an imagedisplay apparatus. More specifically, the present invention relates to aliquid crystal alignment film used for a flat display panel employingliquid crystal for displaying images on television (TV) and computers orthe like, and a method for producing such a liquid crystal alignmentfilm, and also relates to a liquid crystal display apparatus employingthe same and a method for producing such a liquid crystal displayapparatus.

BACKGROUND ART

[0002] Conventionally, an apparatus used as a color liquid crystaldisplay panel generally includes liquid crystal that is injected betweentwo substrates provided with counter electrodes arranged in a matrix viaa liquid crystal alignment film formed by rotary-coating a polyvinylalcohol or a polyimide solution with a spinner or the like.

[0003] For example, the following device was proposed. Thin filmtransistor (TFT) arrays having pixel electrodes are formed on a firstglass substrate beforehand. A plurality of color filters of red, blueand green are formed on a second glass substrate, and common transparentelectrodes are further formed thereon. The surfaces provided with therespective electrodes are coated with a polyvinyl alcohol or a polyimidesolution with a spinner so as to form films. Then, rubbing is performedso as to form liquid crystal alignment films, and the substrates areopposed and attached to each other via spacers with an arbitrary gap.Thereafter, liquid crystal (twist nematic (TN) or the like) is injectedtherebetween so as to form a panel structure. Then, polarizing platesare provided on the front and the back of the panel. While the panel isirradiated with back light from the back side, TFTs are operated. Inthis manner color images are displayed.

[0004] However, in the conventional method for producing an alignmentfilm, polyvinyl alcohol or polyimide is dissolved in an organic solventand the resultant solution is applied by rotary-coating or the like.Then, rubbing is performed with a felt cloth or the like. Therefore,there is a serious problem in that uniformity in the alignment film ispoor in surface step portions or for a large area panel (such as a 14inch display). Moreover, since rubbing is performed, defects aregenerated in the TFTs, and debris generated by rubbing causes defects indisplay.

DISCLOSURE OF INVENTION

[0005] The present invention was carried out in order to solve theabove-mentioned conventional problems, and thus has the object ofproviding a method for forming an alignment film used in a liquidcrystal display panel highly efficiently, uniformly and thinly withoutperforming a rubbing treatment as conventionally performed, andproviding a method for producing a display panel employing the same.

[0006] A first liquid crystal alignment film of the present inventionfor achieving the object is characterized in that a silane-basedsurfactant having linear carbon chains and Si is chemically adsorbed viaa resin film sensitive to energy beams for generating functional groupscontaining active hydrogen by energy beam irradiation formed on apredetermined surface of a substrate, and that the linear carbon chainsare aligned in a specific direction.

[0007] In the above-mentioned liquid crystal alignment film, a filmformed of the surfactant is preferably fixed to an energy beam sensitiveresin film via covalent bonds on the surface of the substrate in astriped pattern. Thus, a liquid crystal alignment film having excellentuniaxial alignment can be obtained.

[0008] In the above-mentioned liquid crystal alignment film, the fixedfilm formed of the surfactant is preferably fixed to the energy beamsensitive resin film via a film having siloxane bonds. This isadvantageous because peeling resistance, namely adhesiveness isimproved.

[0009] In the above-mentioned liquid crystal alignment film, thesilane-based surfactant is preferably a chlorosilane-based surfactantcontaining a linear hydrocarbon group and a chlorosilyl group. As thesilane-based surfactant, a substance comprising a chlorosilyl group(SiCl), an alkoxysilyl group (SiOA, A represents an alkyl group), or anisocyanate silyl group (SiNCO) at the terminal of the molecule can beused. Above all, when a chlorosilane-based surfactant is used, analignment film covalently bonded to the substrate via siloxane bonds canbe produced easily and efficiently.

[0010] In the above-mentioned liquid crystal alignment film, a part ofthe hydrogen of the linear hydrocarbon group of the chlorosilane-basedsurfactant is preferably substituted with at least a fluorine atom. Thisis advantageous because the critical surface energy as the alignmentfilm can be reduced, thereby improving a response performance of liquidcrystal.

[0011] In the above-mentioned liquid crystal alignment film, a pluralityof chlorosilane-based surfactants each having a different molecularlength are preferably mixed and used as the chlorosilane-basedsurfactant containing a linear hydrocarbon group and a chlorosilylgroup. Thus, a film having concavities and convexities on the molecularlevel on its surface can be formed, thus obtaining a liquid crystalalignment film with which the alignment angle (pre-tilt angle) of liquidcrystal can be controlled on the molecular level.

[0012] A second liquid crystal alignment film of the present inventionis a monomolecular film formed on a surface of a substrate provided withdesired electrodes. The molecules constituting the film have a desiredtilt, and are bonded and fixed to the surface of the substrate at oneend while being aligned uniformly in a specific direction.

[0013] In the above-mentioned liquid crystal alignment film, the desiredtilt of the molecules is preferably formed by fixing the moleculesconstituting the film to the substrate by covalent bonds, washing themolecules with an organic solvent, and tilting the substrate in adesired direction so as to drain off the solvent.

[0014] In the above-mentioned liquid crystal alignment film, themolecules constituting the film preferably contain carbon chains orsiloxane bond chains. This is advantageous because the alignmentproperty of the film can be improved.

[0015] In the above-mentioned liquid crystal alignment film, a carbon ofa part of the carbon chain preferably has an optical activity. This isadvantageous because the alignment property of the film can be improvedby irradiation of light.

[0016] In the above-mentioned liquid crystal alignment film, themolecules constituting the film preferably have Si at both ends. This isadvantageous because the film can be bonded to the substrate firmly.

[0017] In the above-mentioned liquid crystal alignment film, themolecules constituting the film are preferably formed by mixing aplurality of types of chemisorption molecules each having a differentmolecular length, and the fixed film preferably has concavities andconvexities on the molecular length level. This is advantageous becausethe tilt angle of liquid crystal can be controlled.

[0018] A third liquid crystal alignment film of the present invention isa monomolecular film formed on a surface of a substrate provided withdesired electrodes. The molecules constituting the film have carbonchains or siloxane bond chains, and at least a part of the carbon chainor the siloxane bond chain contains at least a functional group forcontrolling a surface energy of the film. The production of such aliquid crystal alignment film can provide an alignment film that hasfunctions of controlling the critical surface energy of the alignmentfilm and thus controlling the pre-tilt angle of injected liquid crystal,and aligning the liquid crystal in an arbitrary direction, withoutperforming conventional rubbing.

[0019] In the above-mentioned liquid crystal alignment film, a pluralityof types of silane-based surfactants each having a different criticalsurface energy are preferably mixed and used as the moleculesconstituting the film, so as to control the fixed film to have a desiredcritical surface energy value. This is advantageous because the pre-tiltangle can be controlled.

[0020] In the above-mentioned liquid crystal alignment film, thefunctional group for controlling the surface energy is at least oneorganic group selected from the group consisting of a carbon trifluoridegroup (—CF₃), a methyl group (—CH₃), a vinyl group (—CH═CH₂), an allylgroup (—CH═CH—), an acetylene group (triple bonds of carbon-carbon), aphenyl group (—C₆H₅), an aryl group (—C₆H₄—), a halogen atom, an alkoxygroup (—OR; R represents an alkyl group, preferably an alkyl grouphaving one to three carbons), a cyano group (—CN), an amino group(—NH₂), a hydroxyl group (—OH), a carbonyl group (═CO), an ester group(—COO—) and a carboxyl group (—COOH). This makes it easy to control thecritical surface energy.

[0021] In the above-mentioned liquid crystal alignment film, themolecules constituting the film preferably contain Si at the terminals.This makes it very easy to fix the molecules to the surface of thesubstrate.

[0022] In the above-mentioned liquid crystal alignment film, thecritical surface energy of the film is preferably controlled to be adesired value between 15 mN/m to 56 mN/m. This makes it possible tocontrol the pre-tilt angle of injected liquid crystal to be any angle inthe range from 0 to 90 degrees.

[0023] A fourth liquid crystal alignment film of the present inventionis characterized in that a resin film transparent in the visible lightrange and having energy beam sensitive groups and thermoreactive groupsis formed directly on electrodes or indirectly via an arbitrary thinfilm, and at least the energy beam sensitive groups are reacted andcrosslinked.

[0024] In the above-mentioned liquid crystal alignment film, the energybeam sensitive groups and the thermoreactive groups are preferablyintroduced as side chain groups in the resin film.

[0025] In the above-mentioned liquid crystal alignment film, the energybeam sensitive groups, the thermoreactive groups and hydrocarbon groupsare preferably introduced as side chain groups in the resin film.

[0026] In the above-mentioned liquid crystal alignment film, the surfaceof the resin film preferably has striped concavities and convexities.

[0027] In the above-mentioned liquid crystal alignment film, thethermoreactive groups are preferably reacted and crosslinked.

[0028] In the above-mentioned liquid crystal alignment film, a substancerepresented by (formula 1) is preferably used as the resin film.

[0029] (Formula 1)

[0030] Next, a method for producing the first liquid crystal alignmentfilm of the present invention includes the steps of applying and formingan energy beam sensitive resin film for generating functional groupscontaining active hydrogen by energy beams directly or indirectly via anarbitrary thin film on a predetermined surface of a substrate providedwith electrodes, irradiating the surface of the resin film with energybeams in an arbitrary pattern, contacting the irradiated resin film witha chemisorption solution containing a silane-based surfactant havinglinear carbon chains and Si groups, washing the substrate with a solventincapable of dissolving the resin film, thereby forming one layer of amonomolecular film formed of the surfactant selectively in theirradiated portion, and aligning and fixing the linear carbon chains inthe surfactant molecules.

[0031] In the above-mentioned method, the energy beams are preferably atleast one selected from the group consisting of electron beams, X raysand light with a wavelength of 100 nm to 1 μm. Above all, it isespecially preferable to use ultraviolet rays.

[0032] In the above-mentioned method, the chemisorption solutionpreferably contains at least a chlorosilane-based surfactant comprisinga linear carbon chain and a chlorosilyl group and a solvent that causesno damage to the energy beam sensitive resin film. This is advantageousbecause the underlying photosensitive thin film cannot be injured.

[0033] In the above-mentioned method, the energy beams are preferably atleast one light selected from the group consisting of ultraviolet rays,visible rays and infrared rays, and the energy beam sensitive resin filmis preferably a photosensitive resin film. This makes it very easy toproduce the liquid crystal alignment film.

[0034] In the above-mentioned method, the photosensitive resin film ispreferably a polymer film or a monomer film containing at least oneorganic group selected from the group consisting of a group representedby (formula 2), a group represented by (formula 3) and a grouprepresented by (formula 4). The use of these polymers is advantageousbecause ultraviolet rays can be used as the energy beams.

[0035] Furthermore, when a specific liquid crystal, for example nematicliquid crystal or ferroelectric liquid crystal is incorporated bybonding to a surfactant to be adsorbed, an alignment film having anexcellent alignment controllability can be obtained.

[0036] In the above-mentioned method, a solvent including a carbonfluoride group is preferably used as a nonaqueous solvent. This isadvantageous because the underlying photosensitive substrate cannot beinjured

[0037] A method for producing the second liquid crystal alignment filmof the present invention is a method for producing a monomolecularliquid crystal alignment film including the steps of contacting asubstrate provided with electrodes with a chemisorption solution so asto cause a chemical reaction between molecules of a surfactant in theadsorption solution and a surface of the substrate, thereby bonding andfixing the surfactant molecules to the surface of the substrate at oneend, washing the substrate with an organic solvent, and tilting thesubstrate in a desired direction so as to drain off the solvent, therebyaligning the fixed molecules in the direction in which the solvent wasdrained off.

[0038] Preferably, the above-mentioned method further includes the stepof exposing the substrate to light polarized in a desired direction viaa polarizing plate after the step of aligning the fixed molecules, so asto align the orientations of the surfactant molecules uniformly in aspecific direction at a desired tilt.

[0039] In the above-mentioned method, a silane-based surfactantcontaining linear hydrocarbon groups or siloxane bond chains andchlorosilyl groups, alkoxysilyl groups or isocyanate silyl groups ispreferably used as the surfactant. This makes it possible to produce amonomolecular liquid crystal alignment film efficiently.

[0040] In the above-mentioned method, a plurality of types ofsilane-based surfactants each having a different molecular length aremixed and used as the silane-based surfactant containing linearhydrocarbon groups or siloxane bond chains and chlorosilyl groups,alkoxysilyl groups or isocyanate silyl groups. This is advantageousbecause the alignment angle of the adsorbed and fixed molecules, i.e.,the pre-tilt angle of injected liquid crystal can be controlled.

[0041] In the above-mentioned method, a carbon of a part of thehydrocarbon group preferably has an optical activity. This isadvantageous because alignment can be controlled efficiently at the timeof realignment by irradiation of light.

[0042] In the above-mentioned method, the hydrocarbon group or thesiloxane bond chain preferably contains a halogen atom or a methyl group(—CH₃), a phenyl group (—C₆H₅), a cyano group (—CN), a hydroxyl group(—OH), a carboxyl group (—COOH), an amino group (—NH₂), or a carbontrifluoride group (—CF₃) at the terminal. This makes it possible tocontrol the surface energy of the film.

[0043] In the above-mentioned method, the light that is used forexposure is preferably light having at least one wavelength selectedfrom the group consisting of 436 nm, 405 nm, 365 nm, 254 nm and 248 nmAny light can be used as the light for exposure, as long as the lighthas a wavelength that can be absorbed by the film. However, the lighthaving the above-mentioned wavelength is advantageous because it can beabsorbed by most films.

[0044] In the above-mentioned method, a silane-based surfactantcontaining linear hydrocarbon groups or siloxane bond chains andchlorosilyl groups or isocyanate silyl groups is preferably used as thesurfactant, and a nonaqueous organic solvent containing no water ispreferably used as the washing organic solvent. The use of these isadvantageous in removing unreacted molecules of the surfactantcompletely. At this time, when a photosensitive reactive group such as avinyl group (>C═C<), an acetylene bond group (a triple bond group ofcarbon-carbon) or the like is incorporated into the linear hydrocarbongroup or the siloxane bond chain, and the photosensitive group isallowed to react with light so as to be crosslinked or polymerized atthe time of alignment with light, the heat resistance of the obtainedmonomolecular film can be improved.

[0045] In the above-mentioned method, a solvent containing an alkylgroup, a carbon fluoride group, a carbon chloride group or a siloxanegroup is preferably used as the nonaqueous organic solvent. The use ofthis solvent makes dehydration easy and thus provides a high efficiency.

[0046] In the above-mentioned method, it is preferable to form a filmcontaining a large number of SiO groups before the step of fixing thesurfactant molecules at one end, and then form a monomolecular film viathis film. This makes it possible to obtain a film whose quality isensured.

[0047] A method for producing the third liquid crystal alignment film ofthe present invention includes the steps of contacting a substrateprovided with electrodes with a chemisorption solution produced by usinga silane-based surfactant containing carbon chains or siloxane bondchains, at least a part of the carbon chain or the siloxane bond chaincontaining at least one functional group for controlling a surfaceenergy of a formed film, thereby causing a chemical reaction between thesurfactant molecules in the adsorption solution and the surface of thesubstrate so as to bond and fix the surfactant molecules to the surfaceof the substrate at one end.

[0048] In the above-mentioned method, a silane-based surfactantcontaining linear carbon chains or siloxane bond chains and chlorosilylgroups, alkoxysilyl groups or isocyanate silyl groups is preferably usedas the surfactant.

[0049] In the above-mentioned method, a plurality of types ofsilicon-based surfactants each having a different critical surfaceenergy are preferably mixed and used as the surfactant. This makes itpossible to control the critical surface energy of the film moreprecisely.

[0050] In the above-mentioned method, at least one organic groupselected from the group consisting of a carbon trifluoride group (—CF₃),a methyl group (—CH₃), a vinyl group (—CH═CH₂), an allyl group(—CH═CH—), an acetylene group (triple bonds of carbon-carbon), a phenylgroup (—C₆H₅), an aryl group (—C₆H₄—), a halogen atom, an alkoxy group(—OR; R represents an alkyl group, preferably an alkyl group having oneto three carbons), a cyano group (—CN), an amino group (—NH₂), ahydroxyl group (—OH), a carbonyl group (═CO), an ester group (—COO—) anda carboxyl group (—COOH) is preferably incorporated into the carbonchain or the siloxane bond chain at its terminal, principal chain orside chain. This also makes it possible to control the critical surfaceenergy of the film more precisely.

[0051] Preferably, the above-mentioned method further includes the stepsof washing the substrate with an organic solvent after the step ofbonding and fixing the surfactant molecules to the surface of thesubstrate at one end, and tilting the substrate in a desired directionso as to drain off the solvent, thereby aligning the fixed molecules inthe direction in which the solvent was drained off This makes itpossible to control the tilt angle of injected liquid crystal.

[0052] Preferably, the above-mentioned method further includes the stepof exposing the substrate to light through a polarizing film after thestep of aligning the molecules, so as to realign the molecules in adesired direction. This makes it possible to improve alignmentperformance.

[0053] In the above-mentioned method, a silane-based surfactantcontaining linear carbon chains or siloxane bond chains and chlorosilylgroups or isocyanate silyl groups is preferably used as the surfactant,and a nonaqueous organic solvent containing no water is preferably usedas the washing organic solvent. This makes it possible to provide amonomolecular liquid crystal alignment film having fewer defects.

[0054] At this time, it is advantageous in draining off a solvent to usea solvent containing an alkyl group, a carbon fluoride group, a carbonchloride group or a siloxane group as the nonaqueous organic solvent.

[0055] In the above-mentioned method, it is preferable to perform thestep of forming a film containing a large number of SiO groups beforethe step of fixing the surfactant molecules at one end, and then form amonomolecular liquid crystal film via this film. This makes it possibleto provide a monomolecular alignment film having a higher density.

[0056] A method for producing the fourth liquid crystal alignment filmof the present invention includes the steps of applying and forming aresin film transparent in a visible light range and having energy beamsensitive groups and thermoreactive groups on a predetermined surface ofa substrate provided with electrodes directly or indirectly via anarbitrary thin film, and at least irradiating the resin film with energybeams through an arbitrary mask so as to react and crosslink the energybeam sensitive groups.

[0057] The above-mentioned method preferably includes the steps ofapplying and forming a resin film transparent in a visible light rangeand having energy beam sensitive groups and thermoreactive groups on apredetermined surface of a substrate provided with electrodes directlyor indirectly via an arbitrary thin film, and at least irradiating theresin film with energy beams through an arbitrary mask so as to reactand crosslink the energy beam sensitive groups.

[0058] In the above-mentioned method, the step of reacting andcrosslinking the thermoreactive groups by heating is preferably addedbefore or after the step of reacting and crosslinking the energy beamsensitive groups.

[0059] In the above-mentioned method, the energy beam sensitive groupsare preferably photosensitive groups, and the resin film is preferablyirradiated with ultraviolet rays through a mask so that thephotosensitive groups in the resin film react not only to crosslinkbetween principal chains but also to align and fix side chain groups.

[0060] In the above-mentioned method, a polarizing film or a diffractiongrating is preferably used as the mask for exposure.

[0061] In the above-mentioned method, in the step of exposure, the resinfilm is preferably exposed to light to an extent that concavities andconvexities are generated on the surface thereof.

[0062] Next, a first liquid crystal display apparatus of the presentinvention includes a pair of substrates, electrodes and alignment films,the electrodes being formed on surfaces of substrates, the alignmentfilms being formed thereon, liquid crystal being interposed between thecounter electrodes on the two substrates via the alignment films. Atleast one alignment film is a film in which a silane-based surfactanthaving a linear carbon chain is chemically adsorbed via an energy beamsensitive film for generating a functional group containing activehydrogen by irradiation of energy beams, and the linear carbon chainsare aligned in a specific direction.

[0063] A second liquid crystal display apparatus of the presentinvention has a structure where a film is formed as an alignment filmfor liquid crystal directly on the surface provided with electrodes onat least one substrate of two substrates provided with counterelectrodes or indirectly via another film. The film is a monomolecularfilm formed of a silane-based surfactant having linear carbon chains orsiloxane bond chains, and the molecules constituting the film have adesired tilt and are bonded and fixed to the surface of the substrate atone end while being aligned uniformly in a specific direction. Liquidcrystal is interposed between the counter electrodes on the twosubstrates via the alignment film.

[0064] In the above-mentioned liquid crystal display apparatus, the filmis preferably formed on each of the surfaces of the two substratesprovided with the counter electrodes as the alignment film. This isadvantageous in improving an alignment regulation force on the injectedliquid crystal.

[0065] In the above-mentioned liquid crystal display apparatus, the filmon the surface of the substrate preferably comprises a plurality ofpatterned sections each having a different alignment direction. Thismakes it possible to provide a liquid crystal display apparatus havingmulti-domain alignment easily.

[0066] The above-mentioned liquid crystal display apparatus ispreferably used in an IPS system (an inplane switch system or a lateraldriving system) where the counter electrodes are formed on a surface ofone substrate. This is advantageous because the viewing angle can besignificantly improved.

[0067] A third liquid crystal display apparatus of the present inventionhas a structure where a film is formed as an alignment film for liquidcrystal directly on the surface provided with electrodes on at least onesubstrate of the two substrates provided with counter electrodes orindirectly via another film. The film is constituted by moleculescontaining carbon chains or siloxane bond chains, a part of the carbonchain or the siloxane bond chain containing at least one functionalgroup for controlling a surface energy of the film. Liquid crystal isinterposed between the counter electrodes on the two substrates via thealignment film. This makes it possible to provide a liquid crystaldisplay apparatus in which the critical surface energy of the alignmentfilm is controlled, the pre-tilt angle of the injected liquid crystal iscontrolled, and the liquid crystal is aligned in an arbitrary direction,without performing conventional rubbing.

[0068] In the above-mentioned liquid crystal display apparatus, when thefilm is formed on each of the surfaces of the two substrates providedwith the counter electrodes as the alignment film, it is possible toprovide a liquid crystal display apparatus having a higher contrast.

[0069] In the above-mentioned liquid crystal display apparatus, it isadvantageous to form a plurality of patterned sections each having adifferent alignment direction in the film on the surface of thesubstrate, because the display viewing angle can be significantlyimproved.

[0070] The above-mentioned liquid crystal display apparatus can be usedas a display device of an inplane switch (IPS) type where the counterelectrodes are formed on a surface of one substrate.

[0071] A fourth liquid crystal display apparatus of the presentinvention has a structure where a resin film transparent in a visiblelight range and having energy beam sensitive groups and thermoreactivegroups is formed directly on electrodes or indirectly via an arbitrarythin film, and at least the energy beam sensitive groups are reacted andcrosslinked. The thus obtained liquid crystal alignment film is formedon electrodes on at least one substrate of counter electrodes. Liquidcrystal is interposed between the counter electrodes on the twosubstrates via the resin film.

[0072] Next, a method for producing a first liquid crystal displayapparatus of the present invention includes the steps of applying andforming an energy beam sensitive resin film for generating functionalgroups containing active hydrogen by energy beams directly or indirectlyvia an arbitrary thin film on a first substrate including firstelectrode arrays arranged in a matrix beforehand, irradiating thesurface of the resin film with energy beams in an arbitrary pattern,contacting the substrate with the irradiated resin film with achemisorption solution containing a silane-based surfactant havinglinear carbon chains and Si, washing the substrate with a solventincapable of dissolving the resin film, thereby forming one layer of amonomolecular film formed of the surfactant selectively in theirradiated portion, and aligning and fixing the linear carbon chains,attaching the first substrate including the first electrode arrays to asecond substrate including second electrodes or electrode arrays so thatthe respective electrodes are countered with a predetermined gap, andinjecting predetermined liquid crystal between the first substrate andthe second substrate.

[0073] A method for producing a second liquid crystal display apparatusincludes the steps of contacting a first substrate including firstelectrode arrays arranged in a matrix beforehand with a chemisorptionsolution directly or after forming an arbitrary thin film so as to causea chemical reaction between the surfactant molecules in the adsorptionsolution and the surface of the substrate, thereby bonding and fixingthe surfactant molecules to the surface of the substrate at one end,washing the substrate with an organic solvent, tilting the substrate ina desired direction so as to drain the solvent off the substrate,thereby aligning the fixed molecules in the direction in which thesolvent is drained off, exposing the substrate to light polarized in adesired direction via a polarizing plate so as to align the orientationsof the surfactant molecules uniformly in a specific direction at adesired tilt, attaching the first substrate including the firstelectrodes to a second substrate or a second substrate including secondelectrodes or electrode arrays so that the faces provided with theelectrodes are facing inward with a predetermined gap, and injectingpredetermined liquid crystal between the first substrate and the secondsubstrate.

[0074] In the above-mentioned method, in the step of exposing thesubstrate to light polarized in a desired direction via a polarizingplate so as to align the orientations of the bonded surfactant moleculesuniformly in a specific direction at a desired tilt, it is preferable torepeat the step of exposure with a patterned mask disposed on thepolarizing plate several times, because this can provide a liquidcrystal display apparatus having so called multi-domain alignment wherea plurality of patterned sections each having a different alignmentdirection are formed on one face of the alignment film.

[0075] A method for producing a third liquid crystal display apparatusof the present invention includes the steps of contacting a firstsubstrate including first electrodes arranged in a matrix beforehandwith a chemisorption solution directly or after forming an arbitrarythin film, the chemisorption solution being produced by using asilane-based surfactant containing carbon chains or siloxane bondchains, at least a part of the carbon chain or the siloxane bond chaincontaining at least one functional group for controlling a surfaceenergy of a formed film, so as to cause a chemical reaction between thesurfactant molecules in the adsorption solution and the surface of thesubstrate, thereby bonding and fixing the surfactant molecules to thesurface of the substrate at one end, washing the substrate with anorganic solvent, tilting the substrate in a desired direction so as todrain the solvent off the substrate, thereby aligning the fixedmolecules in the direction in which the solvent is drained off,attaching the first substrate including the first electrode arrays to asecond substrate or a second substrate including second electrodes orelectrode arrays so that the faces provided with the electrodes arefacing inward with a predetermined gap, and injecting predeterminedliquid crystal between the first substrate and the second substrate.This method makes it possible to produce a liquid crystal displayapparatus efficiently.

[0076] In the above-mentioned method, it is preferable to perform thefurther step of exposing the substrate to light polarized in a desireddirection via a polarizing plate so as to align the orientations of thesurfactant molecules uniformly in a specific direction at a desired tiltafter the step of aligning the fixed molecules. This makes it possibleto realize a liquid crystal display apparatus having excellent alignmentcharacteristics.

[0077] In the above-mentioned method, in the step of exposing thesubstrate to light polarized in a desired direction via a polarizingplate so as to align the orientations of the bonded surfactant moleculesuniformly in a specific direction at a desired tilt, it is preferable torepeat the step of exposure with a patterned mask disposed on thepolarizing plate several times so as to form a plurality of patternedsections each having a different alignment direction on one face of thealignment film, because this can provide a liquid crystal displayapparatus having multi-domain alignment.

[0078] A method for producing a fourth liquid crystal display apparatusof the present invention includes the steps of applying and forming aresin film transparent in a visible light range and having energy beamsensitive groups and thermoreactive groups directly or indirectly via anarbitrary thin film on a first substrate including first electrodearrays arranged in a matrix, at least irradiating the resin film withenergy beams through an arbitrary mask so as to react and crosslink theenergy beam sensitive groups, attaching the first substrate includingthe first electrode arrays to a second substrate including secondelectrodes or electrode arrays opposed to the first electrode arrays sothat the respective faces provided with the electrodes are opposed toeach other, and injecting predetermined liquid crystal between the firstsubstrate and the second substrate.

BRIEF DESCRIPTION OF DRAWINGS

[0079]FIG. 1 is a schematic cross-sectional view for illustrating anexposure process in producing a liquid crystal alignment film in Example1 of the present invention.

[0080]FIG. 2 is a schematic view of portion A in FIG. 1 enlarged to amolecular level showing a —COOH group portion formed on a surface of asubstrate by exposure.

[0081]FIG. 3 is a schematic view of portion A in FIG. 1 enlarged to amolecular level showing a lipophilic surface portion in which achemisorption film is formed.

[0082]FIG. 4 is a schematic cross-sectional view showing the orientationstate of liquid crystals in a liquid crystal cell produced by using aliquid crystal alignment film produced in Example 1 of the presentinvention.

[0083]FIG. 5 is a schematic cross-sectional view for illustrating anexposure process in producing a liquid crystal alignment film in Example2 of the present invention.

[0084]FIG. 6 is a schematic view of portion B in FIG. 5 enlarged to amolecular level showing a —COOH group portion formed on a surface of asubstrate by exposure.

[0085]FIG. 7 is a schematic view of portion B in FIG. 5 enlarged to amolecular level showing a lipophilic surface portion in which achemisorption film is formed.

[0086]FIG. 8 is a view for illustrating a process for generatingcarboxyl groups newly by a second exposure in Example 3 of the presentinvention.

[0087]FIG. 9 is a schematic cross-sectional view of a liquid crystalalignment film for illustrating a state where two types of chemisorptionfilms each having a different alignment direction are formed in Example3.

[0088]FIG. 10 is a schematic cross-sectional view enlarged to amolecular level for illustrating a state where a siloxane monomolecularfilm is formed in Example 4 of the present invention.

[0089]FIG. 11 is a schematic cross-sectional view for illustratingproduction of a liquid crystal display apparatus in Example 4 of thepresent invention.

[0090]FIG. 12 is a schematic cross-sectional view for illustrating achemisorption process performed for producing a monomolecular liquidcrystal alignment film in Example 5 of the present invention.

[0091]FIG. 13 is a schematic cross-sectional view for illustrating awashing process in producing a monomolecular liquid crystal alignmentfilm in Example 5 of the present invention.

[0092]FIG. 14 is a schematic view of a cross section enlarged to amolecular level for illustrating a molecular orientation state in amonomolecular liquid crystal alignment film after washing with a solventin Example 5 of the present invention.

[0093]FIG. 15 is a schematic view of an exposure process performed forrealigning adsorbed molecules by light exposure in Example 6 of thepresent invention.

[0094]FIG. 16 is a schematic view for illustrating a molecularorientation state in a monomolecular liquid crystal alignment film afteralignment with light in Example 6 of the present invention.

[0095]FIG. 17 is a schematic view of a cross section enlarged to amolecular level for illustrating a molecular orientation state of amonomolecular chemisorption film after alignment with light in Example 6of the present invention.

[0096]FIG. 18 is a schematic cross-sectional view enlarged to amolecular level for illustrating a state (before a reaction withmoisture in the air) where a chlorosilane monomolecular film is formedin Example 8 of the present invention.

[0097]FIG. 19 is a schematic cross-sectional view enlarged to amolecular level for illustrating a state where a siloxane monomolecularfilm is formed in Example 8 of the present invention.

[0098]FIG. 20 is a schematic cross-sectional view for illustratingproduction of a liquid crystal display apparatus in Example 9 of thepresent invention.

[0099]FIG. 21 shows an absorption spectrum of FTIR measured in adirection perpendicular to a lifting direction in Example 11 of thepresent invention.

[0100]FIG. 22 shows an absorption spectrum of FTIR measured in adirection parallel to the lifting direction in Example 11 of the presentinvention.

[0101]FIG. 23 is a schematic cross-sectional view for illustrating achemisorption process performed for producing a monomolecular liquidcrystal alignment film in Example 12 of the present invention.

[0102]FIG. 24 is a schematic cross-sectional view for illustrating awashing process in producing a monomolecular liquid crystal alignmentfilm in Example 12 of the present invention.

[0103]FIG. 25 is a schematic view of a cross section enlarged to amolecular level for illustrating a molecular orientation state in amonomolecular liquid crystal alignment film after washing with a solventin Example 12 of the present invention.

[0104]FIG. 26 is a schematic view of an exposure process performed forrealigning adsorbed molecules by light exposure in Example 12 of thepresent invention.

[0105]FIG. 27 is a schematic view for illustrating a molecularorientation state in a monomolecular liquid crystal alignment film afteralignment with light in Example 12 of the present invention.

[0106]FIG. 28 is a schematic view of the a cross section enlarged to amolecular level for illustrating a molecular orientation state of amonomolecular chemisorption film after alignment with light in Example12 of the present invention.

[0107]FIG. 29 is a schematic cross-sectional view enlarged to amolecular level for illustrating a state (before a reaction withmoisture in the air) where a chlorosilane monomolecular film is formedin Example 13 of the present invention.

[0108]FIG. 30 is a schematic cross-sectional view enlarged to amolecular level for illustrating a state where a siloxane monomolecularfilm is formed in Example 13 of the present invention.

[0109]FIG. 31 is a schematic cross-sectional view for illustratingproduction of a liquid crystal display apparatus in Example 14 of thepresent invention.

[0110]FIG. 32 is a cross-sectional view showing processes for producinga liquid crystal alignment film in Example 18 of the present invention.

[0111]FIG. 33 is a view showing spectral sensitivity characteristics ofa photosensitive and thermosetting resin in a liquid crystal alignmentfilm in Example 18 of the present invention.

[0112]FIG. 34 is a cross-sectional view of a liquid crystal displaydevice in Example 19 of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0113] A first liquid crystal alignment film of one embodiment of thepresent invention is produced by a method comprising the steps ofapplying and forming an energy beam sensitive resin film for generatingfunctional groups containing active hydrogen by energy beams directly orindirectly via an arbitrary thin film on a predetermined portion on asurface of a substrate provided with electrodes, irradiating the surfaceof the resin film with energy beams in an arbitrary pattern, contactingthe irradiated resin film with a chemisorption solution containing asilane-based surfactant having linear carbon chains and Si groups,washing the resin film with a solvent incapable of dissolving the resinfilm, thereby forming one layer of a monomolecular film formed of thesurfactant selectively in the irradiated portion, and aligning andfixing the linear carbon chains in the surfactant molecules.

[0114] Furthermore, a first liquid crystal display apparatus of oneembodiment of the present invention is produced by a method comprisingthe steps of applying and forming an energy beam sensitive resin filmfor generating functional groups containing active hydrogen by energybeams directly or indirectly via an arbitrary thin film on a firstsubstrate including first electrodes arranged in a matrix beforehand,irradiating the surface of the resin film with energy beams in anarbitrary pattern, contacting the substrate with the irradiated resinfilm with a chemisorption solution containing a silane-based surfactanthaving linear carbon chains and Si, washing the substrate with a solventincapable of dissolving the resin film, thereby forming one layer of amonomolecular film formed of the surfactant selectively in theirradiated portion, and aligning and fixing the linear carbon chains,attaching the first substrate including the first electrodes to a secondsubstrate including second electrodes or electrode arrays so that therespective electrodes are opposed with a predetermined gap, andinjecting predetermined liquid crystal between the first substrate andthe second substrate.

[0115] A second liquid crystal alignment film of one embodiment of thepresent invention is produced by a method comprising at least the stepsof contacting a substrate provided with electrodes with a chemisorptionsolution so as to cause a chemical reaction between the surfactantmolecules in the adsorption solution and the surface of the substrate,thereby bonding and fixing the surfactant molecules to the surface ofthe substrate at one end, washing the substrate with an organic solvent,tilting the substrate in a desired direction so as to drain off thesolvent, thereby firstly aligning the fixed molecules in the directionin which the solvent is drained off, and exposing the substrate to lightpolarized in a desired direction via a polarizing plate so as to alignthe orientations of the surfactant molecules uniformly in a specificdirection at a desired tilt.

[0116] Furthermore, a second liquid crystal display apparatus of oneembodiment of the present invention is produced by a method comprisingat least the steps of contacting a first substrate including firstelectrodes arranged in a matrix beforehand with a chemisorption solutiondirectly or after forming an arbitrary thin film so as to cause achemical reaction between the surfactant molecules in the adsorptionsolution and the surface of the substrate, thereby bonding and fixingthe surfactant molecules to the surface of the substrate at one end,washing the substrate with an organic solvent, tilting the substrate ina desired direction so as to drain the solvent off the substrate,thereby aligning the fixed molecules in the direction in which thesolvent is drained off, exposing the substrate to light polarized in adesired direction via a polarizing plate so as to align the orientationsof the surfactant molecules uniformly in a specific direction at adesired tilt, attaching the first substrate including the firstelectrode arrays to a second substrate or a second substrate includingsecond electrodes or electrode arrays so that the faces provided withthe electrodes are facing inward with a predetermined gap, and injectingpredetermined liquid crystal between the first substrate and the secondsubstrate.

[0117] A third liquid crystal alignment film of one embodiment of thepresent invention is produced by a method comprising at least the stepsof contacting a substrate provided with electrodes with a chemisorptionsolution produced by using a silane-based surfactant containing carbonchains or siloxane bond chains, at least a part of the carbon chain orthe siloxane bond chain containing at least one functional group forcontrolling a surface energy of a formed film, thereby causing achemical reaction between the surfactant molecules in the adsorptionsolution and the surface of the substrate so as to bond and fix thesurfactant molecules to the surface of the substrate at one end.

[0118] Furthermore, a third liquid crystal display apparatus of oneembodiment of the present invention is produced by a method comprisingat least the steps of contacting a first substrate including firstelectrode arrays arranged in a matrix beforehand with a chemisorptionsolution directly or after forming an arbitrary thin film, thechemisorption solution being produced by using a silane-based surfactantcontaining a carbon chain or a siloxane bond chain, at least a part ofthe carbon chain or the siloxane bond chain containing at least onefunctional group for controlling a surface energy of a formed film, soas to cause a chemical reaction between the surfactant molecules in theadsorption solution and the surface of the substrate, thereby bondingand fixing the surfactant molecules to the surface of the substrate atone end, washing the substrate with an organic solvent, tilting thesubstrate in a desired direction so as to drain off the solvent, therebyaligning the fixed molecules in the direction in which the solvent isdrained off, attaching the first substrate including the first electrodearrays to a second substrate or a second substrate including secondelectrodes or electrode arrays so that the faces provided with theelectrodes are facing inward with a predetermined gap, and injectingpredetermined liquid crystal between the first substrate and the secondsubstrate.

[0119] A fourth liquid crystal alignment film of one embodiment of thepresent invention will be generally described below.

[0120] First, a resin film transparent in a visible light range andhaving energy beam sensitive groups and thermoreactive groups is appliedand formed on a predetermined surface of a substrate provided withelectrodes directly or indirectly via an arbitrary thin film. Next, thesubstrate with the resin film is irradiated with energy beams through anarbitrary mask so as to react and crosslink the energy beam sensitivegroups.

[0121] At this time, if the energy beam sensitive groups arephotosensitive groups, and the step of irradiating the film with lightthrough a mask so as to react the photosensitive groups in the film notonly to crosslink between principal chains but also to align and fixside chain groups is included, rubbing is not required as performedconventionally and an ordinary exposure apparatus can be used, thussimplifying the production process of the liquid crystal alignment film.

[0122] Furthermore, when the resin film was irradiated with lightthrough a polarizing film or a diffraction grating as a mask, a liquidcrystal alignment film having striped convexities and concavities wasproduced efficiently.

[0123] At this time, when exposure was performed obliquely through apolarizing film or a diffraction grating, or exposure is performedthrough a polarizing film and then exposure is performed obliquelythrough a diffraction grating, or exposure is performed through adiffraction grating and then exposure is performed obliquely through apolarizing film, a liquid crystal alignment film capable of controllingthe pre-tilt angle of the interposed liquid crystal as well wasproduced. In the process of exposure via the diffraction grating, it wasimportant to expose the photosensitive film to light to an extent thatconvexities and concavities are generated on the surface thereof inorder to stabilize the alignment.

[0124] Furthermore, when heat is applied so as to react thethermoreactive groups before or after radiating energy beams so as tocrosslink the energy beam sensitive groups, the heat resistance of thealignment of the liquid crystal was improved. Electron beams, X rays, orultraviolet rays are usable as the energy beams, but ultraviolet raysprovided higher practicability.

[0125] It is highly advantageous in producing a liquid crystal alignmentfilm to use a substance represented by (formula 1) as the resintransparent in a visible light range and having energy beam sensitivegroups and thermoreactive groups, because the substance has a highultraviolet ray sensitivity, and a thermal crosslinking reaction alsocan be utilized.

[0126] In formula 1, energy beam sensitive benzalacetophenone groups andthermoreactive glycidyl groups are introduced as side chain groups, andhydrocarbon groups (—CH₃) are further introduced as side chain groups.Therefore, compared with substances containing no hydrocarbon groups asside chain groups, the substance represented by (formula 1) provided animproved alignment stability. Furthermore, in this case, it wasimportant to expose the transparent resin film to light to an extentthat convexities and concavities in the range from 1 to 100 nm weregenerated on the surface thereof in order to improve the alignmentstability of the liquid crystal.

[0127] By using the above-mentioned methods, a resin film transparent ina visible light range and having energy beam sensitive groups andthermoreactive groups was formed directly on electrodes or indirectlyvia an arbitrary thin film, and a rubbing-free liquid crystal alignmentfilm formed of a film obtained at least by reacting the energy beamsensitive groups was produced by a remarkably simple method.

[0128] The fourth liquid crystal display apparatus of one embodiment ofthe present invention was produced by a method comprising the steps ofapplying and forming a resin film transparent in a visible light rangeand having energy beam sensitive groups and thermoreactive groupsdirectly or indirectly via an arbitrary thin film on a first substrateincluding first electrodes arranged in a matrix beforehand, at leastirradiating the resin film with energy beams through an arbitrary maskso as to react and crosslink the energy beam sensitive groups, attachingthe first substrate including the first electrodes to a second substrateincluding second electrodes or electrode arrays opposed to the firstelectrode arrays so that the respective faces provided with theelectrodes are opposed to each other, and injecting predetermined liquidcrystal between the first substrate and the second substrate. By theabove-mentioned method, a resin film transparent in a visible lightrange and having energy beam sensitive groups and thermoreactive groupswas formed, and the film was at least irradiated with energy beamsthrough an arbitrary mask so as to react and crosslink the energy beamsensitive groups. The thus obtained film was formed on electrodes on atleast one substrate of the counter electrodes on the two substrates asan alignment film for liquid crystal. Thus, a liquid crystal displayapparatus having a structure in which liquid crystal is interposedbetween the counter electrodes on the two substrates via the film wasproduced with remarkably high efficiency.

[0129] The present invention will be specifically described by way ofexamples.

EXAMPLE 1

[0130] First, as shown in FIG. 1, an energy beam sensitive resin (aphotosensitive resin in this example) was applied onto a surface of aglass substrate 1 provided with transparent electrodes. In this example,a positive resist mainly composed of a novolak resin and comprising anaphthoquinone diazido-based photosensitizer containing the grouprepresented by (formula 2) (e.g., OFPR800 or OFPR5000 manufactured byTokyo Ohka Kogyo Co., Ltd. or AZ1400 or AZ5200 manufactured by SHIPLEY,or a monomolecular film formed of monomers containing naphthoquinonediazido groups can be used) was used as the energy beam sensitive resin.The resin was applied to a thickness of 0.1 to 0.2 μm and dried so as toform a photosensitive film 2. Next, using a mask 3 having a desiredpattern, the film was exposed to ultraviolet rays (365 nm) at about 100mJ/cm². Then, moisture in the air and the resist reacted and thereaction represented by (formula 5) below proceeded in an exposedportion 2′.

[0131] (Formula 5)

[0132] Since the —COOH group generated by the exposure contains activehydrogen, condensation (a dehydrochlorination reaction) was effected incombination with —SiCl groups.

[0133] Then, by using CH₃(CH₂)₁₈SiCl₃ as a silane-based surfactantcontaining linear hydrocarbon groups and Si (hereinafter, referred to asa chemisorption compound) and dissolving it in a nonaqueous solvent at aconcentration of about 1 wt %, a chemisorption solution was prepared. Asthe nonaqueous solvent, Afulude (manufactured by Asahi Glass Co., Ltd.,a fluorine-based solvent) solution was used. Since this solvent isinactive with respect to a positive resist, it does not injure theresist film even if the resist film is in contact with the solvent. Thethus prepared solution was used as an adsorption solution, and theexposed substrate 4 was immersed in the adsorption solution in a dryatmosphere (a relative humidity of 30% or less) for 5 minutes.Thereafter, the substrate was lifted from the solution, and washed witha fluorine based nonaqueous solvent (e.g., Fluorinert PF5080 (3M productname)) (since this solvent is also inactive with respect to a positiveresist, it does not injure the resist film even if the resist film is incontact with the solvent.) Then, the exposed portion on the surface ofthe substrate contains a large number of —COOH (carboxyl groups) 5 (FIG.2, which is an enlarged view of portion A of FIG. 1), so that adehydrochlorination reaction was effected between the SiCl groups of thesubstance containing hydrocarbon groups and chlorosilyl groups and thecarboxyl groups, thereby generating bonds represented by (formula 6)below selectively in the exposed portion. The line breadth and the pitchwere 0.3 μm.

[0134] (Formula 6)

[0135] In the above-described treatment, a monomolecular chemisorptionfilm 6 containing hydrocarbon was formed in a thickness of about 25 Å(2.5 nm) selectively in the exposed portion by being chemically bondedvia siloxane covalent bonds, and the treated portion became lipophilic.At this time, the linear carbon chains in the chemisorption film werealigned substantially perpendicular to the substrate (FIG. 3, which isan enlarged view of portion A of FIG. 1). The critical surface energy ofthe chemisorption film was 20 mN/m.

[0136] Then, two substrates in this state were set in such a manner thatthe chemisorption films were acing each other, so as to assemble aliquid crystal cell having a 20 micron gap. Thereafter, nematic liquidcrystal (ZLI4792 manufactured by Merck & Co., Inc.) was injected. Whenthe orientation state was observed, it was confirmed that the injectedliquid crystal molecules were aligned along the chemically adsorbedmolecules and substantially perpendicular to the substrate. In otherwords, this monomolecular film exhibited a perpendicular alignmentfunction for liquid crystal. At this time, since no monomolecular filmwas formed in an unexposed portion, liquid crystal was aligned notuniformly but at random. More specifically, when the substrate providedwith such an alignment film was in contact with liquid crystal, as shownin FIG. 4, the liquid crystal molecules 7 were partially inserted in thegaps of long carbon chains 8 of the monomolecular adsorption film. Thus,the orientation of the liquid crystal was controlled as a whole. On theother hand, since such an alignment regulation force was not present inthe portion provided with no monomolecular film, namely the unexposedportion, the liquid crystal molecules 7′ were not aligned uniformly.

[0137] In place of the surfactant that is a chemisorption compound, aplurality of silane-based surfactants mixed in a predetermined ratio(e.g., two surfactants each having a different length of a linear carbonchain) were mixed so as to cause chemisorption at the same time. In thiscase, voids on the molecular level were generated in the monomolecularfilm, and the liquid crystal molecules were aligned along the voids.Therefore, it was confirmed that the orientation angle of the liquidcrystal was controlled by changing the composition. More specifically,when a silane-based surfactant having an arbitrary substituent at a partof its linear long carbon chain and a trichlorosilyl group at the otherend was mixed with a silane-based surfactant having an arbitrarysubstituent at a part of its short carbon chain and a trichlorosilylgroup at the other end at a predetermined ratio so as to causeadsorption, it was possible to change the orientation characteristics.

[0138] Furthermore, when a silane-based surfactant containing polymericgroups, bonded to liquid crystal molecules similar to the liquid crystalto be incorporated, in a part of substituent (e.g., nematic liquidcrystal portion) was mixed with a silane-based surfactant containingshort carbon chains and polymeric groups at a predetermined ratio, so asto cause adsorption and polymerization, an alignment film havingexcellent orientation characteristics especially with respect tospecific liquid crystal to be injected was obtained. In particular, inthe case where those molecules similar to the molecules of the liquidcrystal be injected were of ferroelectric liquid crystal, when asilane-based surfactant having a ferroelectric liquid crystal portionwas mixed with a silane-based surfactant having short carbon chains at apredetermined ratio so as to cause adsorption, a monomolecularadsorption and alignment film having an excellent response rate wasformed. As the ferroelectric liquid crystal, azomethine-based,azoxy-based or ester-based liquid crystal was usable.

[0139] A material for chemisorption is not limited to the silane-basedsurfactant shown in Example 1, but any material can be used as long asit contains groups having a bonding property with respect to —OH groups(e.g., chlorosilyl groups, isocyanate silyl groups, alkoxysilyl groupsor the like).

[0140] For example, even when a silane surfactantCF₃—(CH₂)_(m)—C═C—(CH₂)_(n)—SiCl₃ (m: an integer of 0 to 8; n: aninteger, most preferably of about 10 to 25) orCF₃—(CF₂)_(p)—(CH₂)_(m)—C═C—(CH₂)_(n)—SiCl₃ (p: an integer of 0 to 7; m:an integer of 0 to 4; and n: an integer of 1 to 8) containing F(fluorine) at a part of the linear hydrocarbon chain was used, amonomolecular adsorption film having an alignment function was produced.In the case where CF₃—(CH₂)_(m)—C═C—(CH₂)_(n)—SiCl₃ was used, thecritical surface energy of the chemisorption film was 15 mN/m. In thecase where CF₃—(CF₂)_(p)—(CH₂)_(m)—C═C—(CH₂)_(n)—SiCl₃ was used, thecritical surface energy of the chemisorption film was 8 mN/m. Thus,especially when F atoms were introduced, the surface energy of thealignment film became small and the response characteristic of liquidcrystal was improved. The critical surface energy in the portion (on thesurface of the resin) provided with no chemisorption film (monomolecularfilm) was 25 mN/m.

[0141] Any other resist (polymer films) or surfactant (monomer films)than the novolak resist containing naphthoquinone diazido can be used,as long as it has functional groups that generate active hydrogen byirradiation of a variety of energy beams.

[0142] For example, the monomer or the polymer represented by (formula7) below containing (formula 3), or the monomer or the polymerrepresented by (formula 8) below containing (formula 4) can be used.

[0143] Herein, a decarboxylation reaction proceeds in the grouprepresented by (formula 3) with ultraviolet rays, and a reaction withmoisture in the air is effected, so that amino groups containing activehydrogen are generated, as shown in (formula 9) below.

[0144] On the other hand, the group represented by (formula 4) isdegraded by ultraviolet rays, and sulfonic groups containing activehydrogen are generated, as shown in (formula 10) below.

[0145] In the above example, CH₃(CH₂)₁₈SiCl₃ was used as the hydrocarbonbased surfactant. However, other compounds as shown below were usable.CH₃(CH₂)_(n)SiCl₃ (n is an integer, preferably of 7 to 24)CH₃(CH₂)_(p)Si(CH₃)₂(CH₂)_(q)SiCl₃ (p and q are integers, preferably of0 to 10) CH₃COO(CH₂)_(m)SiCl₃ (m is an integer, preferably of 7 to 24)

[0146] Furthermore, in place of the hydrocarbon based surfactant, acarbon fluoride-based surfactant, such as CF₃(CF₂)₇(CH₂)₂SiCl₃,CF₃CH₂O(CH₂)₁₅SiCl₃, CF₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅SiCl₃,F(CF₂)₄(CH₂)₂Si(CH₃)₂(CH₂)₉SiCl₃, F(CF₂)₈(CH₂)₂Si(CH₃)₂(CH₂)₉SiCl₃,CF₃COO(CH₂)₁₅)SiCl₃, CF₃(CF₂)₅(CH₂)₂SiCl₃ or the like, was usable.

EXAMPLE 1-2

[0147] The same experiment as Example 1 was performed, except thatCH₃(CH₂)₁₄SiCl₃ and NC(CH₂)₁₄SiCl₃, which contain a linear hydrocarbongroup comprising one functional group for controlling the surface energyof a film at the terminal and Si, were used as the silane-basedsurfactant after the exposure of the entire face (they were mixed at amole ratio of 1:1).

[0148] As a result of the reaction with the chlorosilane-basedsurfactant, a monomolecular chemisorption film was formed selectively inthe portion on the surface of the substrate where hydroxyl groups havebeen generated by exposure. This monomolecular film was chemicallybonded thereto via siloxane bonds in a thickness of about 1.5 nm. Thecritical surface energy of the chemisorption film was about 27 mN/m.

[0149] Furthermore, two substrates in this state were used so as to beset so that the chemisorption films were facing each other. Thus, aliquid crystal cell having a 20 micron gap was assembled so that ananti-parallel orientation was obtained, and then nematic liquid crystal(ZLI4792 manufactured by Merck & Co., Inc.) was injected. When observingthe orientation state in the portion where the monomolecular film wasformed, the injected liquid crystal molecules were aligned substantiallyalong the chemically adsorbed molecules at a pre-tilt angle of 65° withrespect to the substrate in the direction opposite to the direction inwhich the substrate had been lifted from the washing solution(hereinafter, referred to as a lifting direction).

[0150] At this time, when the composition of CH₃(CH₂)₁₄SiCl₃ andNC(CH₂)₁₄SiCl₃ was changed in the range of 1:0 to 0:1 (preferably 10:1to 1:50), the critical surface energy was changed from 20 mN/m to 29mN/m, and the pre-tilt angle was able to be controlled arbitrarily inthe range from 90° to 40°. Furthermore, when a surfactant containingfluorine as a chemisorption compound such as CF₃(CF₂)₅(CH₂)₂SiCl₃ wasadded, the critical surface energy was reduced to 15 mN/m.

EXAMPLE 2

[0151] First, a positive resist 22 (e.g., AZ1400 manufactured bySHIPLEY) mainly composed of a novolak resin and comprising anaphthoquinone diazido based photosensitizer containing the grouprepresented by (formula 2) was applied onto a surface of a glasssubstrate 21 provided with TFT arrays having pixel electrodes on theirsurfaces to a thickness of 0.1 to 0.2 μm and dried so as to form a film.The critical surface energy of the film was 28 mN/m. Next, using aphotomask 23 for dividing each pixel (a polarizing plate or adiffraction grating may be disposed on the mask for dividing the pixelfor the purpose of improving the alignment property of the adsorptionfilm), the positive resist was exposed to light of 435 nm at 100 mJ/cm²(FIG. 5). As a result, the resist reacted with moisture in the air in anexposed portion 22′ so as to proceed the reaction represented by(formula 5). At this time, since —COOH group 25 generated by theexposure contains active hydrogen (FIG. 6, which is a partially enlargedview of portion B of FIG. 5), a dehydrochlorination reaction waseffected in combination with SiCl groups.

[0152] Then, by mixing a nonaqueous solvent with a substance comprisinghydrocarbon groups and chlorosilyl groups, for example, by dissolvingCH₃(CH₂)₁₃SiCl₃ in Afulude (manufactured by Asahi Glass Co., Ltd, afluorine based solvent) in a concentration of about 1 wt %, anadsorption solution was prepared. Then, the exposed substrate 24 wasimmersed in the adsorption solution in a dry atmosphere (a relativehumidity of 30% or less) for 5 minutes.

[0153] Thereafter, the substrate was lifted from the solution, andwashed with a fluorine based solvent (e.g., Fluorinert PF5080 (3Mproduct name)). Since the exposed portion on the surface of thesubstrate contains a large number of —COOH (carboxyl groups), adehydrochlorination reaction was caused between the SiCl groups of thesubstance containing hydrocarbon groups and chlorosilyl groups and thecarboxyl groups, thereby generating bonds represented by (formula 11)below selectively in the exposed portion. Thus, a chemisorption film 26containing hydrocarbon groups was formed in a thickness of about 15 Å(1.5 nm) selectively in the exposed portion through chemical bonds (FIG.7, which is a partially enlarged view of portion B of FIG. 5). Thetreated portion became water-repelling and oil-repelling.

[0154] Furthermore, after an unexposed portion was entirely exposed (theexposure may be performed through a mask) (FIG. 8), the substrate wasimmersed for 5 minutes in a second adsorption reagent, for example anadsorption solution prepared by dissolving CH₃(CH₂)₉SiCl₃ and CH₃SiCl₃at a mole ratio of 1:5 so as to have the same concentration as above.Thereafter, the substrate was lifted from the solution, and washed witha fluorine based solvent (e.g., Fluorinert PF5080 (3M product name)).Then, since the secondly exposed portion on the surface of the substratecontains a large number of —COOH (carboxyl groups), adehydrochlorination reaction was effected between the SiCl groups ofCH₃(CH₂)₉SiCl₃ and CH₃SiCl₃ and the carboxyl groups. Thus, achemisorption film 27 containing hydrocarbon groups was formed in athickness of about 10 Å (1.0 nm) selectively in the exposed portionthrough chemical bonds FIG. 9). At this time, active groups were nolonger present in the firstly adsorbed portion, and a monomolecular filmwas formed, so that the second adsorption was not effected at all. Thus,the firstly exposed and adsorbed portion 26 and the portion 27 having adifferent alignment direction were formed in one pixel. In the exposureprocess, when a polarizing plate or a diffraction grating was disposedon the mask, a monomolecular film having the adsorbed molecules alignedin stripes was formed selectively. Furthermore, the critical surfaceenergy of the monomolecular film at this time was 20 mN/m.

[0155] Then, two substrates 28 were set so that the chemisorption filmswere facing each other, so as to assemble a liquid crystal cell having a20 micron gap. Thereafter, nematic liquid crystal (ZLI4792 manufacturedby Merck & Co., Inc.) was injected. When the orientation state wasobserved, it was confirmed that one pixel was constituted by amulti-domain having a portion where the injected liquid crystalmolecules were aligned along the chemically adsorbed molecules andsubstantially perpendicular to the substrate and a portion where theinjected liquid crystal molecules were aligned obliquely with respect tothe substrate. In order words, in this case, since the pixel portion wasdivided into two, an alignment film having two domains of differentalignment directions of liquid crystal was produced.

[0156] In order to increase the number of divisions, the exposure andadsorption process using a mask is repeated a desired number of times.

EXAMPLE 3

[0157] After exposure and before the process of chemisorption of themolecules comprising linear hydrocarbon groups in Example 1, thesubstrate was immersed in an adsorption solution prepared by dissolvinga compound containing a plurality of chlorosilyl groups in a dryatmosphere. Then, a dehydrochlorination reaction was effected betweenhydroxyl groups of the carboxyl groups generated on the surface of theresist and chlorosilyl groups of the compounds containing a plurality ofchlorosilyl groups. Thereafter, when a reaction with water was allowedto be effected, the remaining chlorosilyl groups changed to hydroxylgroups, so that a chemisorption film comprising a large number ofhydroxyl groups on its surface was formed.

[0158] For example, SiCl₄ was used as the silyl compound containing aplurality of chloro groups, and dissolved in Fluorinert FC40 (3M productname) so as to prepare an adsorption solution. Then, the exposedsubstrate was immersed in the adsorption solution. As a result, since—COOH groups were formed in the exposed portion of the resist 32′, adehydrochlorination reaction was effected on the surface so as to form(formula 12) and/or (formula 13). Thus, chlorosilane molecules werefixed to the surface of the substrate in a pattern via —SiO— bonds.

[0159] Thereafter, when the substrate was washed with a nonaqueoussolvent, e.g., Fluorinert FX3252 (3M product name), the SiCl₄ moleculesthat had not reacted with the resist were removed, and further allowedto react with water. Then, a siloxane monomolecular adsorption film 33represented by (formula 14) and (formula 15) was obtained on the surface(FIG. 10).

[0160] When the process of washing with a nonaqueous solvent, e.g.,Fluorinert FX3252 (3M product name) was omitted, a polysiloxanechemisorption film was formed.

[0161] Furthermore, since the thus obtained siloxane monomolecular film33 was firmly bonded to the resist via the chemical bonds of —SiO—, itwas not peeled off. Furthermore, the obtained monomolecular film has alarge number of SiOH bonds on its surface. The SiOH bonds were generatedin a number about twice or three times the original number of —COOHgroups. The treated portions in this state were highly hydrophilic.Then, in this state, when the chemisorption process of the samesubstance comprising hydrocarbon groups as in Example 1 was performed, amonomolecular chemisorption film comprising hydrocarbon as shown in FIG.1 was formed in a thickness of about 25 Å (2.5 nm) selectively in theexposed portion by being chemically bonded thereto through covalentbonds of siloxane via the siloxane monomolecular film. At this time,since the adsorption sites (OH groups in this case) on the surface ofthe substrate were about twice or three times as many as that in Example1, the density of the adsorbed molecules was larger than that ofExample 1. The treated portion became lipophilic. The molecules of thechemisorption film in this case, although having a different density,were aligned substantially perpendicular to the substrate in the samemanner as the molecules shown in FIG. 3.

[0162] Then, two substrates in this state were set so that thechemisorption films were facing each other, so as to assemble a liquidcrystal cell having a 20 micron gap. Thereafter, nematic liquid crystal(ZLI4792 manufactured by Merck & Co., Inc.) was injected. When theorientation state was observed, it was confirmed that the injectedliquid crystal molecules were aligned along the chemically adsorbedmolecules and substantially perpendicular to the substrate. In otherwords, this monomolecular film exhibited a perpendicular alignmentfunction for liquid crystal. At this time, liquid crystal was notaligned uniformly in an unexposed portion.

[0163] As the silyl compound containing a plurality of chloro groups,compounds other than SiCl₄ described above, such as Cl—(SiCl₂O)₂—SiCl₃,or SiHCl₃, SiH₂Cl₂, or Cl—(SiCl₂O)_(n)—SiCl₃ (n is an integer), wereusable.

EXAMPLE 4

[0164] Next, a production process in actually producing a liquid crystaldisplay device by using the liquid crystal alignment film describedabove will be described with reference to FIG. 11.

[0165] First, the resin containing energy beam sensitive groupsrepresented by (formula 2) was diluted to 5 wt % in ethylcellosolveacetate so as to prepare a sensitizing solution (e.g., a novolak basedpositive resist such as AZ1400 may be used) beforehand. As shown in FIG.11, a first substrate 43 includes first electrode arrays 41 mounted in amatrix and transistor arrays 42 for driving the electrodes. A secondsubstrate 46 includes color filter arrays 44 and second electrodes 45opposed to the first electrode arrays. The prepared sensitizing solutionwas applied onto the both electrodes on the first substrate and thesecond substrate by rotary-coating, so as to form a photosensitive resinfilm (a novolak based positive resist film) in the same manner asExample 1. Thereafter, heating was performed at 100° C. for 10 minutesso as to remove the solvent to some extent. Then, a diffraction gratingof 1000 slits/mm (a polarizing plate can be used) was used as a mask andarranged so that the grating was parallel to the electrode pattern.Then, light having a wavelength of 435 nm (g rays) (at 28 mJ/cm² afterpassing through the mask) was radiated at 500 W by using an extra-highpressure mercury lamp from the vertical direction for 5 seconds, so asto react naphthoquinone diazide in the photosensitive novolak basedpositive resist. As a result, —COOH groups were generated in the exposedportion in proportion to the extent of the exposure. Then, when thechemisorption process was performed in the same manner as in Example 1,a liquid crystal alignment film 47 in which linear hydrocarbon groupsare aligned along the electrode pattern was produced. Next, the firstand the second substrates 43 and 46 were positioned so that they wereopposed to each other, and fixed with spacers 48 and an adhesive 49 withabout a 5 micron gap. Thereafter, the TN liquid crystal 50 was injectedbetween the first and the second substrates, and polarizing plates 51and 52 were provided. Thus, a display device was completed.

[0166] Such a device was able to display images in the direction shownby arrow A by being entirely irradiated with backlight 53 and by drivingeach transistor with video signals.

EXAMPLE 5

[0167] A glass substrate 61 (comprising a large number of hydroxylgroups on its surface) provided with transparent electrodes on itssurface was prepared and washed and sufficiently degreased beforehand.Next, by using silane-based surfactants containing linear hydrocarbongroups as carbon chains and Si (hereinafter, referred to as achemisorption compound), CN(CH₂)₁₄SiCl₃ and CH₃SiCl₃ (mixed at a moleratio of 1:10), and dissolving them in a nonaqueous solvent in aconcentration of about 1 wt %, a chemisorption solution was prepared. Asthe nonaqueous solvent, sufficiently dehydrated hexadecane was used. Thethus prepared solution was used as an adsorption solution 62, and thesubstrate 61 was immersed in (or coated with) the adsorption solution 62in a dry atmosphere (a relative humidity of 30 % or less) for 50 minutes(FIG. 12). Thereafter, the substrate was lifted from the solution, andwashed with sufficiently dehydrated n-hexane 63, which is a nonaqueoussolvent. Then, the substrate was lifted from the washing solution whilebeing tilted in a desired direction, the solution was drained off, andthe substrate was then exposed to the air containing moisture (FIG. 13).Arrow 65 is a lifting direction. In the series of processes, adehydrochlorination reaction was effected between SiCl groups of thechlorosilane-based surfactant and hydroxyl groups of the surface of thesubstrate, thereby generating the bonds represented by (formulae 16 and17). Furthermore, a reaction was effected with moisture in the air,thereby generating the bonds represented by (formulae 18 and 19).

[0168] By performing the above-described treatment, as a result of thereaction with the chlorosilane-based surfactants, a monomolecularchemisorption film 64 was formed in the portion on the surface of thesubstrate having hydroxyl groups. This monomolecular film was chemicallybonded thereto via siloxane covalent bonds in a thickness of about 1 nm.The linear carbon chains of CN(CH₂)₁₄Si— in the chemisorption film werealigned at a tilt angle of 20° in a direction substantially opposite toa direction 65 in which the substrate had been lifted from the washingsolution FIG. 14). In order words, the orientation of the adsorbed andfixed molecules were generally aligned uniformly for the firstalignment. By changing the composition of CN(CH₂)₁₄SiCl₃ and CH₃SiCl₃ inthe range from 1:0 to 0:1 (preferably 10:1 to 1:50), the tilt angle wasable to be controlled arbitrarily in the range from 0° to 90°. In orderto form a film selectively, the adsorption solution 62 can be printed onthe surface of the substrate 61 in a desired pattern with a printer.Furthermore, after the surface of the substrate is covered with a resistselectively beforehand, the chemisorption process may be performed andthe resist may be removed. In this case, since the chemically adsorbedfilm is not peeled off by an organic solvent, a resist that can bedissolved and removed by an organic solvent is used.

EXAMPLE 6

[0169] The substrate obtained in Example 5 was used. A polarizing plate(HNP′B) 66 (manufactured by POLAROID) was disposed on the substrate sothat the polarizing direction was substantially orthogonal to a liftingdirection. Then, they were irradiated with light 67 of 365 nm (i rays)by an extra-high pressure mercury lamp at 100 mJ/cm². In order to alignthe orientations of the adsorbed molecules uniformly in one direction,it is necessary to deviate the polarizing direction by some degrees,preferably several degrees or more from 90°, rather than allowing thepolarizing direction to intersect the lifting direction exactly by 90°(at the maximum, the polarizing direction may be parallel to thedirection in which the solution had been drained off). If they intersecteach other exactly by 90°, the molecules may be oriented in twodirections (FIG. 15). In FIG. 15, arrow 73 denotes the polarizingdirection.

[0170] Thereafter, when the orientation of the linear carbon chains inthe monomolecular chemisorption film 64′ was examined, the tilt angleremained unchanged, but the orientation 68 was changed to a directionsubstantially orthogonal to the lifting direction. In addition, thenon-uniformity of the orientation was alleviated compared with that atthe first alignment (FIGS. 16 and 17). In the Figure, reference numeral69 denotes transparent electrodes.

[0171] In order to change the orientation selectively, a process inwhich a desired mask was disposed on the polarizing plate and thenexposure was performed was repeated a plurality of times. Thus, amonomolecular liquid crystal alignment film having different alignmentdirections in a pattern was produced easily.

[0172] In this example, as a solvent containing no water for washing, asolvent containing an alkyl group such as a hydrocarbon based n-hexanewas used, but any other solvents can be used, as long as it contains nowater and dissolves a surfactant. For example, in addition to that, asolvent containing a carbon fluoride group, a carbon chloride group or asiloxane group, such as Freon 113, chloroform, hexamethyldisiloxane orthe like, was usable.

EXAMPLE 7

[0173] The same experiment as Example 5 was performed, except thatCH₃(CH₂)₁₄SiCl₃ and NC(CH₂)₁₄SiCl₃ comprising linear hydrocarbon groupshaving one functional group for controlling surface energy of a film atthe terminal and Si were used as the silane-based surfactant (by beingmixed at a mole ratio of 1:1).

[0174] As a result of the reaction with the chlorosilane-basedsurfactant, a monomolecular chemisorption film was formed selectively inthe portion on the surface of the substrate where hydroxyl groups havebeen generated. This monomolecular film was chemically bonded theretovia siloxane covalent bonds in a thickness of about 1.5 nm. The criticalsurface energy of the chemisorption film was about 27 mN/m.

[0175] Furthermore, two substrates in this state were used and set sothat the chemisorption films were facing each other. Thus, a liquidcrystal cell having a 20 micron gap was assembled so that ananti-parallel orientation was obtained, and then nematic liquid crystalCM4792 manufactured by Merck & Co., Inc.) was injected. When observingthe orientation state in the portion where the monomolecular film wasformed, the injected liquid crystal molecules were aligned substantiallyalong the chemically adsorbed molecules with a pre-tilt angle of 65°with respect to the substrate in the direction opposite to the directionin which the substrate had been lifted from the washing solution.

[0176] At this time, when the composition of CH₃(CH₂)₁₄SiCl₃ andNC(CH₂)₁₄SiCl₃ was changed in the range of 1:0 to 0:1 preferably 10:1 to1:50), the critical surface energy was changed from 20 mN/m to 29 mN/m,and the pre-tilt angle was able to be controlled arbitrarily in therange from 90° to 40°. Furthermore, when a surfactant containingfluorine such as CF₃(CF₂)₅(CH₂)₂SiCl₃ was added as a chemisorptioncompound, the critical surface energy was reduced to 15 mN/m.

EXAMPLE 8

[0177] Before the process of chemisorption of the surfactant moleculescomprising carbon chains and siloxane bond chains in Example 5, anadsorption solution was prepared by dissolving a compound containing aplurality of chlorosilyl groups, and the substrate was immersed in theadsorption solution in a dry atmosphere. Then, a dehydrochlorinationreaction was effected between hydroxyl groups present on the surface ofthe substrate and chlorosilyl groups of the compound containing aplurality of chlorosilyl groups. Thereafter, a reaction with water wasallowed to be effected and the remaining chlorosilyl groups changed tohydroxyl groups, so that a chemisorption film comprising a large numberof hydroxyl groups on its surface was formed.

[0178] For example, SiCl₄ was used as the silyl compound containing aplurality of chloro groups, and dissolved in n octane so as to preparean adsorption solution. Then, the substrate was immersed in theadsorption solution in a dry atmosphere. As a result, since —OH groupswere present on the surface, a dehydrochlorination reaction was effectedat the interface so as to form (formula 20) and/or (formula 21). Thus,chlorosilane molecules 71 were fixed to the surface of the substrate via—SiO— bonds.

[0179] Thereafter, when the substrate was washed with a nonaqueoussolvent such as chloroform, extra SiCl₄ molecules that had not reactedwith the substrate were removed (FIG. 18). When the substrate was takenout in the air so as to react with water, a siloxane monomolecularadsorption film 72 containing a large number of SiO bonds represented by(formula 22) and/or (formula 23) was obtained on the surface (FIGS. 19).

[0180] When the process of washing with a nonaqueous solvent such aschloroform was omitted, a polysiloxane chemisorption film was formed.

[0181] Furthermore, since the thus obtained siloxane monomolecular film72 was firmly bonded to the substrate via the chemical bonds of —SiO—,it was not peeled off. Furthermore, the obtained monomolecular film hasa large number of SiOH bonds on its surface. The SiOH bonds weregenerated in a number about twice or three times the original number of—OH groups. The treated portion in this state was highly hydrophilic.Then, in this state, when the chemisorption process was performed byusing the same surfactant as in Example 5, the same monomolecularchemisorption film comprising carbon chains obtained as a result of thereaction of the surfactant as in FIG. 12 was formed in a thickness ofabout 1 nm by being chemically bonded through covalent bonds of siloxanevia the siloxane monomolecular film. At this time, since the adsorptionsites (OH groups in this case) on the surface of the substrate beforethe adsorption of the surfactant were about twice or three times as manyas that in Example 5, the density of the adsorbed molecules was largerthan that of Example 5. Furthermore, the treated portion becamelipophilic. The molecules of the chemisorption film in this case,although having a different molecular density, were aligned in thedirection opposite to the lifting direction, namely the direction inwhich the solution had been drained off.

[0182] Next, two substrates in this state were used, and a polarizingplate was disposed on the substrate so that the polarizing direction wassubstantially orthogonal to the lifting direction. Then, they wereirradiated with a KrF excimer laser of 248 nm at 80 mJ/cm². Thereafter,when the orientation of the linear carbon chains in the monomolecularchemisorption film was examined, the tilt angle was 25°, which wasslightly larger, and the orientation was changed to a directionsubstantially orthogonal to the lifting direction. In addition,non-uniformity of the orientation was alleviated.

[0183] Then, two substrates in this state were set so that thechemisorption films were facing each other, so as to assemble a liquidcrystal cell having a 20 micron gap so that an anti-parallel orientationwas obtained. Thereafter, nematic liquid crystal (ZLI4792 manufacturedby Merck & Co., Inc.) was injected. When the orientation state wasobserved, it was confirmed that the injected liquid crystal moleculeswere aligned along the chemically adsorbed molecules and substantiallyat about 25° with respect to the substrate.

[0184] As the silyl compound containing a plurality of chloro groups,compounds other than SiCl₄ described above, such as Cl—(SiCl₂O)₂—SiCl₃,or SiHCl₃, SiH₂Cl₂, or Cl—(SiCl₂O)_(n)—SiCl₃ (n is an integer), wereusable.

EXAMPLE 9

[0185] Next, a production process in actually producing a liquid crystaldisplay device by using the above-described aliment film will bedescribed with reference to FIG. 20.

[0186] First, as shown in FIG. 20, a first substrate 83 includes firstelectrode arrays 81 mounted in a matrix and transistor arrays 82 fordriving the electrodes. A second substrate 86 includes color filterarrays 84 and second electrodes 85 opposed to the first electrodearrays. A chemisorption solution was applied onto the first substrateand the second substrate by rotary-coating, so as to form achemisorption film in the same manner as Example 5. Thereafter, apolarizing plate HNP′B (manufactured by POLAROID) was used and disposedso that the polarizing direction was parallel to the electrode pattern.Then, light having a wavelength of 365 nm (i rays) (at 3.6 mJ/cm².safter passing through the polarizing plate) was radiated at 500 W byusing an extra-high pressure mercury lamp from the vertical directionfor 20 seconds. Thus, a liquid crystal alignment film 87 in which linearhydrocarbon groups were realigned along the electrode pattern wasproduced as in Example 5. Next, the first and the second substrates 83and 86 were positioned so that the respective electrodes were opposed,and fixed with spacers 88 and an adhesive 89 with about a 5 micron gap.Thereafter, the TN liquid crystal 90 was injected between the first andthe second substrates, and polarizing plates 91 and 92 were provided.Thus, a display device was completed.

[0187] Such a device was able to display images to the direction shownby arrow A by being entirely irradiated with backlight 93 and by drivingeach transistor with video signals.

EXAMPLE 10

[0188] In the light realignment process in Example 9, when the processof disposing a patterned mask for dividing each pixel into four sectionsin a checkerboard pattern on the polarizing plate for exposure wascarried out twice, four sections each having a different alignmentdirection in a pattern were formed in one pixel. Thus, when thesubstrate provided with this alignment film was used, the viewing angleof the liquid crystal display apparatus was significantly improved.

EXAMPLE 11

[0189] As a chemisorption compound, CH₃(CH₂)₁₈SiCl₃ and CH₃(CH₂)₃SiCl₃were used (by being mixed at a mole ratio of 1:1), and dissolved in anonaqueous solvent in a concentration of about 1 wt % so as to prepare achemisorption solution. As the nonaqueous solvent, sufficientlydehydrated hexadecane was used. The thus prepared solution was used asan adsorption solution, and the substrate provided with electrodes wasimmersed in the adsorption solution in a dry atmosphere (a relativehumidity of 30% or less) for 1 hour in the same manner as in Example 5.Thereafter, the substrate was lifted from the solution, and washed withsufficiently dehydrated water-free n-hexane, which was a nonaqueoussolvent. Then, the substrate was lifted from the washing solution whilebeing tilted in a desired direction, the solution was drained off, andthe substrate was then exposed to the air containing moisture in thesame manner as in FIG. 13.

[0190] Thereafter, FTIR was used to examine and analyze the firstalignment. The results are shown in FIGS. 21 and 22. As seen from FIGS.21 and 22, the absorption spectrum measured in a direction perpendicularto a lifting direction (FIG. 21) has a different absorption pattern fromthe absorption spectrum measured in a direction parallel to a liftingdirection (FIG. 22). In FIG. 21, the absorption intensity at 2930 cm⁻¹due to the asymmetric stretching vibration of CH₂ is twice theabsorption intensity at 2857 cm⁻¹ due to the symmetric stretchingvibration of CH₂, whereas in FIG. 22, the absorption intensity at 2929cm⁻¹ due to the asymmetric stretching vibration of CH₂ is about 1.7times the absorption intensity at 2859 cm⁻¹ due to the symmetricstretching vibration of CH₂. Furthermore, the absorption peak at 2930cm⁻¹ shifted to red, and the absorption peak at 2857 cm⁻¹ shifted toblue. This indicates that the hydrocarbon chains of the adsorbed andfixed molecules are aligned in a direction parallel to the liftingdirection, namely in the direction in which the solution had beendrained off.

[0191] Furthermore, two substrates in this state were used so as to beset so that the chemisorption films were facing each other. Thus, aliquid crystal cell having a 20 micron gap was assembled so that ananti-parallel orientation was obtained, and then nematic liquid crystal(ZLI4792 manufactured by Merck & Co., Inc.) was injected and apolarizing plate was used. When observing the orientation state, theinjected liquid crystal molecules were aligned substantially in adirection in which the solution had been drained off, namely thedirection opposite to the direction in which the substrate had beenlifted from the washing solution. Furthermore, the cell was sandwichedbetween two polarizing plates combined under crossed Nicole. Then, inthe cases where a voltage of 20 volts was applied and no voltage wasapplied to electrodes, namely in the cases where the cell was on andoff, the transmittance was measured. As a result, a contrast of 358 wasobtained. This indicates that the lifting alignment process aloneprovides an alignment property of a practical level.

[0192] In Examples 6, 8, 9 and 10, light of 365 nm which is i rays froman extra-high pressure mercury lamp or light of 248 nm obtainable from aKrF excimer laser was used as light for exposure. However, light of 436nm, 405 mn or 254 nm can be used, depending on the degree of absorptionof light by a film substance. In particular, light of 248 nm or 254 nmprovides a high alignment efficiency because it is absorbed by mostsubstances readily.

[0193] Furthermore, in the above-described example, as the silane-basedsurfactant comprising linear hydrocarbon groups or siloxane bond chainsand chlorosilyl groups, alkoxysilyl groups or isocyanate silyl groups, achlorosilane-based surfactant comprising a cyano group on one end of itsmolecule and a chlorosilyl group at the other end, mixed with achlorosilane-based surfactant comprising a methyl group and achlorosilyl group, was used. In order words, two types ofchlorosilane-based surfactants having different molecular lengths wereused by being mixed. However the present invention is not limitedthereto, and a chlorosilane-based surfactant comprising a halogen atomor a methyl group (—CH₃), a phenyl group (—C₆H₅), a cyano group (—CN),or a carbon trifluoride group (—CF₃) at the terminal of a hydrocarbongroup, or a chlorosilane-based surfactant in which a carbon of a part ofa hydrocarbon group in its molecule has an optical activity (in thiscase, in particular, the molecules were aligned efficiently), as shownbelow, was usable.

[0194] Furthermore, a chlorosilane-based surfactant represented byHa(CH₂)_(n)SiCl₃ (Ha represents a halogen atom such as chlorine,bromine, iodine, fluorine, or the like, and n is an integer, preferablyof 1 to 24) can be used. Moreover, the following compounds can be used.

[0195] (1) CH₃(CH₂)_(n)SiCl₃ (n is an integer, preferably of 0 to 24.)

[0196] (2) CH₃(CH₂)_(p)Si(CH₃)₂(CH₂)_(q)SiCl₃ (p and q are integers,preferably of 0 to 10.)

[0197] (3) CH₃COO(CH₂)_(m)SiCl₃ (m is an integer, preferably of 7 to24.)

[0198] (4) C₆H₅(CH₂)_(n)SiCl₃ (n is an integer, preferably of 0 to 24.)

[0199] (5) CN(CH₂)_(n)SiCl₃ (n is an integer, preferably of 0 to 24.)

[0200] (6) Cl₃Si(CH₂)_(n)SiCl₃ (n is an integer, preferably of 3 to 24.)

[0201] (7) Cl₃Si(CH₂)₂(CF₂)_(n)(CH₂)₂SiCl₃ (n is an integer, preferablyof 1 to 10.)

[0202] (8) Br(CH₂)₈SiCl₃

[0203] (9) CH₃(CH₂)₁₇SiCl₃

[0204] (10) CH₃(CH₂)₅Si(CH₃)₂(CH₂)₈SiCl₃

[0205] (11) CH₃COO(CH₂)₁₄SiCl₃

[0206] (12) C₆H₅(CH₂)₈SiCl₃

[0207] (13) CN(CH₂)₁₄SiCl₃

[0208] (14) Cl₃Si(CH₂)₈SiCl₃

[0209] (15) Cl₃Si(CH₂)₂(CF₂)₄(CH₂)₂SiCl₃

[0210] (16) Cl₃Si(CH₂)₂(CF₂)₆(CH₂)₂SiCl₃

[0211] (17) CF₃CF₃(CF₂)₇(CH₂)₂SiCl₃

[0212] (18) CF₃CF₃CH₂O(CH₂)₁₅Si(CH₃)₂Cl

[0213] (19) CF₃CF₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅SiCl₃

[0214] (20) F(CCF₃(CF₂)₄(CH₂)₂Si(CH₃)₂(CH₂)₉SiCl₃

[0215] (21) F(CF₂)₈(CH₂)₂Si(CH₃)₂(CH₂)₉SiCl₃

[0216] (22) CF₃COO(CH₂)₁₅SiCH₃Cl₂

[0217] (23) CF₃(CF₂)₅(CH₂)₂SiCl₃

[0218] (24) CH₃CH₂CHC*H₃CH₂OCO(CH₂)₁₀SiCl₃

[0219] (25) CH₃CH₂CHC*H₃CH₂OCOC₆H₄OCOC₆H₄O(CH₂)₅SiCl₃,

[0220] wherein C* indicates an optically active carbon.

[0221] Furthermore, the following compounds comprising a siloxane bondchain and a chlorosilyl group, or an alkoxysilyl group or an isocyanatesilyl group were usable (in this case as well, a film having a highalignment was obtained).

[0222] (26) ClSi(CH₃)₂OSi(CH₃)₂OSi(CH₃)2OSi(CH₃)₂Cl

[0223] (27) Cl₃SiOSi(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂OSiCl₃

[0224] Furthermore, in addition to the chlorosilane-based surfactant,silane-based surfactants comprising an alkoxysilyl group or anisocyanate silyl group as shown below were usable.

[0225] (28) Ha(CH₂)_(n)Si(OCH₃)₃ (Ha represents a halogen atom such aschlorine, bromine, iodine, fluorine, or the like, and n is an integer,preferably of 1 to 24.)

[0226] (29) CH₃(CH₂)_(n)Si((NCO)₃ (n is an integer, preferably of 0 to24.)

[0227] (30) CH₃(CH₂)_(p)Si(CH₃)₂(CH₂)_(q)Si(OCH₃)₃ (p and q areintegers, preferably of 0 to 10.)

[0228] (31) HOOC(CH₂)_(m)Si(OCH₃)₃ (m is an integer, preferably of 7 to24.)

[0229] (32) H₂N(CH₂)_(m)Si(OCH₃)₃ (m is an integer, preferably of 7 to24.)

[0230] (33) C₆H₅(CH₂)_(n)Si(NCO)₃ (n is an integer, preferably of 0 to24.)

[0231] (34) CN(CH₂)_(n)Si(OC₂H₅)₃ (n is an integer preferably of 0 to24.)

EXAMPLE 12

[0232] A glass substrate 101 (comprising a large number of hydroxylgroups on its surface) provided with transparent electrodes on itssurface was prepared, and washed and sufficiently degreased beforehand.Next, by using silane-based surfactants containing a linear hydrocarbongroup comprising a functional group for controlling the surface energyof a film at the terminal and Si hereinafter, referred to as achemisorption compound), CH₃(CH₂)₁₄SiCl₃ and NC(CH₂)₁₄SiCl₃ (mixed at amole ratio of 1:1), and dissolving them in a nonaqueous solvent in aconcentration of about 1 wt %, a chemisorption solution was prepared. Asthe nonaqueous solvent, sufficiently dehydrated hexadecane was used. Thethus prepared solution was used as an adsorption solution 102, and thesubstrate 101 was immersed in (or coated with) the adsorption solution102 in a dry atmosphere (a relative humidity of 30% or less) for aboutone hour (FIG. 23). Thereafter, the substrate was lifted from thesolution, and washed with sufficiently dehydrated water-free n-hexane103, which is a nonaqueous solution. Then, the substrate was lifted fromthe washing solution while being tilted in a desired direction, thesolution was drained off, and the substrate was then exposed to the aircontaining moisture FIG. 24). In the series of processes, adehydrochlorination reaction was effected between SiCl groups ofchlorosilane-based surfactant and hydroxyl groups on the surface of thesubstrate, thereby generating the bonds represented by (formulae 24 and25). Furthermore, a reaction was effected with moisture in the air,thereby generating the bonds represented by (formulae 26 and 27).

[0233] By performing the above-described treatment, as a result of thereaction with the chlorosilane-based surfactants, a monomolecularchemisorption film 104 was formed in the portion on the surface of thesubstrate having hydroxyl groups. This monomolecular film was chemicallybonded thereto via covalent bonds of siloxane in a thickness of about1.5 nm. The critical surface energy of the chemisorption film at thistime was about 27 mN/m.

[0234] Furthermore, two substrates in this state were used so as to beset so that the chemisorption films were facing each other. Thus, aliquid crystal cell having a 20 micron gap was assembled so that ananti-parallel orientation was obtained, and then nematic liquid crystal(ZLI4792 manufactured by Merck & Co., Inc.) was injected. When observingthe orientation state, the injected liquid crystal molecules werealigned substantially along the chemically adsorbed molecules with apre-tilt angle of about 65° with respect to the substrate in thedirection opposite to the direction 105 in which the substrate had beenlifted from the washing solution (FIG. 25).

[0235] At this time, when the composition of CH₃(CH₂)₁₄SiCl₃ andNC(CH₂)₁₄SiCl₃ was changed in the range of 1:0 to 0:1 (preferably 10:1to 1:50), the critical surface energy was changed from 20 mN/m to 29mN/m, and the pre-tilt angle was able to be controlled arbitrarily inthe range from 90° to 40°. Furthermore, when a surfactant containingfluorine as a chemisorption compound such as CF₃(CF₂)₅(CH₂)₂SiCl₃ wasadded, the critical surface energy was reduced to 15 mN/m.

[0236] In order to form a film selectively, the adsorption solution 102was able to be printed on the surface of the substrate 101 in a desiredpattern with a printer. Furthermore, after the surface of the substrateis covered with a resist selectively beforehand, the chemisorptionprocess may be performed and the resist be removed. In this case, sincethe chemically adsorbed film is not peeled off by an organic solvent, aresist that can be dissolved and removed by an organic solvent is used.

[0237] As described above, in this example, the silane-based surfactantsthat provide films each having a different critical surface energy andhave the same carbon chain length as —(CH₂)₁₄— were used. However, whenthe surfactants that have different carbon chain length (e.g.,—(CH₂)_(n)—; n is an integer of 1 to 30) were mixed and used, analignment regulation force was further enhanced.

[0238] Next, two substrates in this state were used, and a polarizingplate (HNP′B) 106 (manufactured by POLAROID) was disposed on thesubstrate so that the polarizing direction 113 was substantiallyorthogonal to a lifting direction 105. Then, light 107 having awavelength of 365 nm (i rays) (at 3.6 mW/cm² after passing through thepolarizing plate) was radiated at 500 W by using an extra-high pressuremercury lamp at 50 mJ.

[0239] At this time, in order to align the orientations of the adsorbedmolecules uniformly in one direction, it is necessary to deviate thepolarizing direction by some degrees, preferably several degrees or morefrom 90°, rather than allowing the polarizing direction to intersect thelifting direction exactly by 90°. In this case, at the maximum, thepolarizing direction 113 may be parallel to the direction in which thesolution had been drained off. If they intersect each other exactly by90°, the molecules may be oriented in two directions (FIG. 26).Thereafter, when the orientation of the linear carbon chains in themonomolecular chemisorption film 104′ was examined, the tilt angle andthe critical surface energy remained unchanged, but the orientation 108was changed to a direction substantially parallel to the polarizingdirection 113. In addition, the non-uniformity of the orientation wasalleviated compared with that at the first alignment (FIGS. 27 and 28).In the Figure, reference numeral 109 denotes transparent electrodes.

[0240] In order to change the orientation selectively, a process inwhich a desired mask was disposed on the polarizing plate, and thenexposure was performed was repeated a plurality of times. Thus, amonomolecular liquid crystal alignment film having different alignmentdirections in a pattern was produced easily.

[0241] In this example, as a solvent containing no water for washing, ahydrocarbon based n-hexane containing an alkyl group was used, but anyother solvent can be used, as long as it contains no water and dissolvesa surfactant. Other examples include a solvent containing a carbonfluoride group, a carbon chloride group or a siloxane group, such asFreon 113, chloroform, hexamethyldisiloxane or the like.

EXAMPLE 13

[0242] Before the process of chemisorption of the surfactant moleculescomprising carbon chains and siloxane bond chains in Example 12, anadsorption solution was prepared by dissolving a compound containing aplurality of chlorosilyl groups, and the substrate was immersed in theadsorption solution in a dry atmosphere. Then, a dehydrochlorinationreaction was effected between hydroxyl groups contained on the surfaceof the substrate and the chlorosilyl groups of the compound containing aplurality of chlorosilyl groups. Thereafter, when a reaction with waterwas allowed to be effected, the remaining chlorosilyl groups changed tohydroxyl groups, so that a chemisorption film comprising a large numberof hydroxyl groups on its surface was formed.

[0243] For example, SiCl₄ was used as the silyl compound containing aplurality of chloro groups, and dissolved in n octane so as to preparean adsorption solution. Then, the substrate was immersed in theadsorption solution in a dry atmosphere. As a result, since —OH groupswere present on the surface, a dehydrochlorination reaction was effectedat the interface so as to form (formula 28) and/or (formula 29). Thus,chlorosilane molecules 111 were fixed to the surface of the substratevia —SiO— bonds.

[0244] Thereafter, when the substrate was washed with a nonaqueoussolvent such as chloroform, extra SiCl₄ molecules that had not reactedwith the substrate were removed (FIG. 29). Furthermore, the substratewas taken out in the air so as to react with water. Then, a siloxanemonomolecular adsorption film 112 containing a large number of SiO bondsrepresented by (formula 30) and/or (formula 31) was obtained on thesurface (FIG. 30).

[0245] When the process of washing with a nonaqueous solvent such aschloroform was omitted, a polysiloxane chemisorption film (silica film)was formed.

[0246] Furthermore, since the thus obtained siloxane monomolecular film112 was firmly bonded to the substrate via chemical bonds of —SiO—, itwas not peeled off. Furthermore, the obtained monomolecular film has alarge number of SiOH bonds on its surface. The SiOH bonds were generatedin a number about twice or three times the original number of —OHgroups. The treated portion in this state was highly hydrophilic. Then,in this state, when the chemisorption process was performed by using thesame surfactant as in Example 12, the same monomolecular chemisorptionfilm comprising carbon chains obtained as a result of the reaction ofthe surfactant as in FIG. 23 was formed in a thickness of about 1.5 nmby being chemically bonded through covalent bonds of siloxane via thesiloxane monomolecular film 112. At this time, since the adsorptionsites (OH groups in this case) on the surface of the substrate beforeadsorption were about twice or three times as many as that in Example12, the density of the adsorbed molecules was higher than that ofExample 12. The treated portion became lipophilic. The molecules of thechemisorption film in this case, although having a different moleculardensity, were aligned in the direction opposite to the liftingdirection, namely the direction in which the solution had been drainedoff.

[0247] Next, a substrate in this state was used, and a polarizing platewas disposed on the substrate so that the polarizing direction wassubstantially orthogonal to the lifting direction. Then, a KrF excimerlaser of 248 nm was radiated at 80 mJ/cm². Thereafter, when theorientation of the linear carbon chains in the monomolecularchemisorption film was examined, the tilt angle was 87°, which wasslightly larger, and the orientation was changed to a directionsubstantially orthogonal to the lifting direction. In addition,non-uniformity of the orientation was alleviated. The critical surfaceenergy at this time was 28 mN/m.

[0248] Then, two substrates in this state were set so that thechemisorption films were facing each other, so as to assemble a liquidcrystal cell having a 20 micron gap so that an anti-parallel orientationwas obtained. Thereafter, nematic liquid crystal (ZLI4792 manufacturedby Merck & Co., Inc.) was injected. When the orientation state wasobserved, it was confirmed that the injected liquid crystal moleculeswere aligned along the chemically adsorbed molecules and substantiallyat a pre-tilt angle of about 46° with respect to the substrate.

[0249] As the silyl compounds containing a plurality of chloro groups,compounds other than SiCl₄ such as Cl—(SiCl₂O)₂—SiCl₃, or SiHCl₃,SiHCl₃, SiH₂Cl₂, or Cl—(SiCl₂O)_(n)—SiCl₃ (n is an integer) were usable.

EXAMPLE 14

[0250] In the case where ClSi(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂Cl andCH₃(CH₂)₁₄SiCl₃ were mixed in the range from 1:0 to 0:1 and used as thechemisorption substance in place of CH₃(CH₂)₁₄SiCl₃ andNC(CH₃)₂(CH₂)₁₄SiCl₃ in Example 12, the critical surface energy wascontrolled in the range from 35 mN/m to 21 mN/m in accordance with themixing ratio. When a cell was assembled and the same liquid crystal wasinjected, the pre-tilt angle was controlled in the range from 5° to 90°.

[0251] Furthermore, when ClSi(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂Clcomprising a linear siloxane bond chain was mixed with CH₃(CH₂)₁₄SiCl₃comprising a linear hydrocarbon chain at a desired ratio so as to form afilm, a monomolecular chemisorption film comprising the moleculesrepresented by (formula 32) and (formula 33) below, depending on themixing ratio, was obtained.

EXAMPLE 15

[0252] In place of CH₃(CH₂)₁₄SiCl₃ and NC(CH₃)₂(CH₂)₁₄SiCl₃ in Example12, HOOC(CH₂)₁₆Si(OCH₃)₃ and Br(CH₂)₈Si(OCH₃)₃ were mixed in the rangefrom 1:0 to 0:1 and used as the chemisorption substance, and reflux wasperformed at 100° C. for two hours during chemisorption. In this case,the critical surface energy was controlled in the range from 56 mN/m to31 mN/mn in accordance with the mixing ratio. Furthermore, when a cellwas assembled and the same liquid crystal was injected, the pre-tiltangle was controlled in the range from 0° to 28°.

EXAMPLE 16

[0253] In place of CH₃(CH₂)₁₄SiCl₃ and NC(CH₃)₂(CH₂)₁₄SiCl₃ in Example12, CH₃CH₂C*HCH₃CH₂OCO(CH₂)₁₀SiCl₃ (wherein C* is an asymmetric carbon)and CH₃SiCl were mixed in the range from 1:0 to 1:20 and used as thechemisorption substance so as to produce the same alignment film. Inthis case, the critical surface energy was controlled in the range from36 mN/m to 41 mN/m in accordance with the mixing ratio. Furthermore,when a cell was assembled and the same liquid crystal was injected, thepre-tilt angle was controlled in the range from 3° to 0.1°.

EXAMPLE 17

[0254] Next, a production process in actually producing a liquid crystaldisplay device by using the above-described liquid crystal alignmentfilm will be described with reference to FIG. 31.

[0255] First, as shown in FIG. 31, a first substrate 123 includes firstelectrode arrays 121 mounted in a matrix and transistor arrays 122 fordriving the electrodes. A second substrate 126 includes color filterarrays 124 and second electrodes 125 opposed to the first electrodearrays. According to the same procedures as in Example 16, a preparedchemisorption solution was applied onto the first substrate and thesecond substrate so as to form a monomolecular chemisorption film havinga critical surface energy of 36 mN/m.

[0256] Thereafter, a polarizing plate HNP′B (manufactured by POLAROID)was used and disposed so that the polarizing direction was parallel tothe electrode pattern. Then, light having a wavelength of 365 nm (irays) (at 3.6 mJ/cm² after passing through the polarizing plate) wasradiated at 500 W by using an extra-high pressure mercury lamp from thevertical direction for 20 seconds. As a result, a liquid crystalalignment film 127 having a critical surface energy of 37 mN/m in whichlinear hydrocarbon groups were realigned along the electrode pattern wasproduced as in Example 16. Next, the first and the second substrates 123and 126 were positioned so that the respective electrodes were opposed,and fixed with spacers 128 and an adhesive 129 with about a 5 microngap. Thereafter, the TN liquid crystal 130 was injected between thefirst and the second substrates, and polarizing plates 131 and 132 wereprovided. Thus, a display device was completed. In this case, thepre-tilt angle of the injected liquid crystal was 3 degrees.

[0257] Such a device was able to display images in the direction shownby arrow A by being entirely irradiated with backlight 133 and bydriving each transistor with video signals.

EXAMPLE 18

[0258] In the light realignment process in Example 17, when the processof disposing a patterned mask for dividing each pixel into four sectionsin a checkerboard pattern on the polarizing plate for exposure wascarried out twice, four sections having different alignment directionsin a pattern were obtained in one pixel. Thus, when the substrateprovided with this alignment film was used, the viewing angle of theliquid crystal display apparatus was significantly improved.

[0259] In Examples 12 through 18, light of 365 nm, which is i rays, froman extra-high pressure mercury lamp or light of 248 nm obtainable from aKrF excimer laser was used as light for exposure. However, light of 436nm, 405 nm or 254 nm can be used, depending on the degree of absorptionof light by a film substance. In particular, light of 248 nm or 254 nmprovides a high alignment efficiency because it is absorbed by mostsubstances readily.

[0260] Furthermore, in the above-described example, as the silane-basedsurfactant comprising a linear hydrocarbon group or a siloxane bondchain and a chlorosilyl group, or an alkoxysilyl group or an isocyanatesilyl group, a chlorosilane-based surfactant comprising a cyano group onone end of its molecule and a chlorosilyl group at the other end wasmixed with a chlorosilane-based surfactant comprising a methyl group anda chlorosilyl group. In order words, two types of chlorosilanesurfactants having different surface energies were mixed and used.However, the present invention is not limited thereto. By combiningvarious surfactants having different surface energies, various alignmentfilms having different surface energies were produced. For example, achlorosilane-based surfactant substituted with at least one organicgroup selected from the group consisting of a carbon trifluoride group(—CF₃), a methyl group (—CH₃), a vinyl group (—CH═CH₂), an allyl group(—CH═CH—), an acetylene group (triple bonds of carbon-carbon), a phenylgroup (—C₆H₅), an aryl group (—C₆H₄—), a halogen atom, an alkoxy group(—OR; R represents an alkyl group, especially preferably an alkyl grouphaving one to three carbons), a cyano group (—CN), an amino group(—NH₂), a hydroxyl group (—OH), a carbonyl group (═CO), an ester group(—COO—) and a carboxyl group (—COOH), or a hydrocarbon group having anoptical activity at the terminal of its hydrocarbon group, as shownbelow, was usable.

[0261] Furthermore, a chlorosilane-based surfactant represented byHa(CH₂)_(n)SiCl₃ (Ha represents a halogen atom such as chlorine,bromine, iodine, fluorine, or the like, and n is an integer, preferablyof 1 to 24) can be used. Moreover, the following compounds can be used.

[0262] (1) CH₃(CH₂)_(n)SiCl₃ (n is an integer, preferably of 0 to 24.)

[0263] (2) CH₃(CH₂)_(p)Si(CH₃)₂(CH₂)_(q)SiCl₃ (p and q are integers,preferably of 0 to 10.)

[0264] (3) CH₃COO(CH₂)_(m)SiCl₃ (m is an integer, preferably of 7 to24.)

[0265] (4) C₆H₅(CH₂)_(n)SiCl₃ (n is an integer, preferably of 0 to 24.)

[0266] (5) CN(CH₂)_(n)SiCl₃ (n is an integer, preferably of 0 to 24.)

[0267] (6) Cl₃Si(CH₂)_(n)SiCl₃ (n is an integer, preferably of 3 to 24.)

[0268] (7) Cl₃Si(CH₂)₂(CF₂)_(n)(CH₂)₂SiCl₃ n is an integer, preferablyof 1 to 10.)

[0269] Furthermore, in addition to the chlorosilane-based surfactant,silane-based surfactants comprising an alkoxysilyl group or anisocyanate silyl group as shown below were usable.

[0270] (8) Ha(CH₂)_(n)Si(OCH₃)₃ (Ha represents a halogen atom such aschlorine, bromine, iodine, fluorine, or the like, and n is an integer,preferably of 1 to 24.)

[0271] (9) CH₃(CH₂)_(n)Si(NCO)₃ (n is an integer, preferably of 0 to24.)

[0272] (10) CH₃(CH₂)_(p)Si(CH₃)₂(CH₂)_(q)Si(OCH₃)₃ (p and q areintegers, preferably of 0 to 10.)

[0273] (11) HOOC(CH₂)_(m)Si(OCH₃)₃ (m is an integer, preferably of 7to24.)

[0274] (12) H₂N(CH₂)_(m)Si(OCH₃)₃ (m is an integer, preferably of 7 to24.)

[0275] (13) C₆H₅(CH₂)_(n)Si(NCO)₃ (n is an integer, preferably of 0 to24.)

[0276] (14) CN(CH₂)_(n)Si(OC₂H₅)₃ (n is an integer, preferably of 0 to24.)

[0277] More specifically, the following compounds can be used.

[0278] (1) Br(CH₂)₈SiCl₃

[0279] (2) CH₂═CH(CH₂)₁₇SiCl₃

[0280] (3) CH₃(CH₂)₈—CO—(CH₂)₁₀SiCl₃

[0281] (4) CH₃(CH₂)₅—COO—(CH₂)₁₀SiCl₃

[0282] (5) CH₃(CH₂)₈—Si(CH₃)₂—(CH₂)₁₀SiCl₃

[0283] (6) CH₃(CH₂)₁₇SiCl₃

[0284] (7) CH₃(CH₂)₅Si(CH₃)₂(CH₂)₈SiCl₃

[0285] (8) CH₃COO(CH₂)₁₄SiCl₃

[0286] (9) C₆H₅(CH₂)₈SiCl₃

[0287] (10) CN(CH₂)₁₄SiCl₃

[0288] (11) Cl₃Si(CH₂)₈SiCl₃

[0289] (12) Cl₃Si(CH₂)₂(CF₂)₄(CH₂)₂SiCl₃

[0290] (13) Cl₃Si(CH₂)₂(CF₂)₆(CH₂)₂SiCl₃

[0291] (14) CF₃CF₂(CF₂)₇(CH₂)₂SiCl₃

[0292] (15) (CF₃)₂CHO(CH₂)₁₅Si(CH₃)₂Cl

[0293] (16) CF₃CF₂(CH₂)₂Si(CH₃)₂(CH₂)₁₅SiCl₃

[0294] (17) CF₃(CF₂)₄(CH₂)₂Si(CH₃)₂(CH₂)₉SiCl₃

[0295] (18) CF₃(CF₂)₇(CH₂)₂Si(CH₃)₂(CH₂)₉SiCl₃

[0296] (19) CF₃COO(CH₂)₁₅SiCH₃Cl₂

[0297] (20) CF₃(CF₂)₅(CH₂)₂SiCl₃

[0298] (21) CH₃CH₂CHC*H₃CH₂OCO(CH₂)₁₀SiCl₃ (C* represents an opticallyactive asymmetric carbon.)

[0299] (22) CH₃CH₂CHC*H₃CH₂OCOC₆H₄OCOC₆H₄O(CH₂)₅SiCl₃

[0300] (23) a compound represented by (formula 34) below

[0301] (Formula 34)

CH₃(CH₂)₈—C≡C—(CH₂)₁₀SiCl₃

[0302] (24) a compound represented by (formula 35) below

[0303] (Formula 35)

CH₃(CH₂)₈—C≡C—C≡C—(CH₂)₁₀SiCl₃

[0304] Furthermore, the following compounds comprising a siloxane bondchain and a chlorosilyl group, or an alkoxysilane group or an isocyanatesilane group were usable. In this case as welt a film having a highalignment was obtained.

[0305] (25) ClSi(CH₃)₂OSi(CH₂)₂OSi(CH₃)₂OSi(CH₃)₂Cl

[0306] (26) Cl₃SiOSi(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂OSiCl₃

EXAMPLE 19

[0307] Hereinafter, a fourth liquid crystal alignment film of thepresent invention will be described in detail with reference to theaccompanying drawings.

[0308] FIGS. 32 (a) to (d) are cross-sectional views showing aproduction process of a fourth liquid crystal alignment film of thepresent invention. Hereinafter, the present example will be describedaccording to FIGS. 32(a) to (d).

[0309] First, 4′ methacryloyloxy chalcone (4′ MC) and glycidylmethacrylate (GMA) were copolymerized at a mole ratio of 1:4 so as toprepare a resin transparent in a visible light range as shown in(formula 1), where a photosensitive benzalacetophenone group and athermocrosslinking glycidyl group and methyl group were introduced asside chain groups (i.e., a resin having an energy beam sensitive groupand a thermoreactive group) beforehand. Then, the resin was diluted to0.5% in cyclohexanone so as to prepare a sensitizing solution.

[0310] Next, the sensitizing solution was applied directly (orindirectly via a insulating thin film such as SiO₂ or the like) to apredetermined portion on the surface of a glass substrate 142 previouslyprovided with transparent electrodes 141 formed of ITO, as shown in FIG.32 (a), by using a dipping method (or a rolling coater or flexography).Thus, as shown in FIG. 32 (b), a photosensitive and thermosetting film143 was formed.

[0311] Thereafter, the film was heated at 100° C. for 10 minutes so asto remove most of the solvent (the thickness at this time was about 300nm). Next, as shown in FIG. 32 (c), a diffraction grating 144 of 1000slits/mm was used as a mask (a polarizing plate can be used, where it isnecessary to prolong an exposure time because the transmittance ispoor), and disposed so that it was parallel to the electrode pattern.Then, as energy beams, ultraviolet rays 145 having a wavelength of 365nm (i rays) (at 28mJ/cm² after passing through the mask) were radiatedfrom the vertical direction at 500 W by using an extra-high pressuremercury lamp for 5 seconds, so as to react and crosslink thephotosensitive benzalacetophenone group. As a result, convexities andconcavities of about 30 to 40 nm were formed on the surface of the filmalong the diffraction grating at a pitch of 1000 slits/mm.

[0312]FIG. 33 shows the spectral sensitivity characteristics of thephotosensitive film.

[0313] In this state, a liquid crystal cell was assembled with a 20micron gap. Then, nematic liquid crystal (ZLI4792 manufactured by Merck& Co., Inc.) was injected. When the orientation state was observed, itwas confirmed that the liquid crystal was aligned in a directionorthogonal to the diffraction grating pattern. Furthermore, it wasconfirmed that the pre-tilt angle of the injected liquid crystal wascontrolled by the exposure amount.

[0314] On the other hand, in the exposure process, after performingexposure for 3 seconds by using the diffraction grating, a commerciallyavailable polarizing plate 146 for UV rays (HNP′B manufactured byPOLAROID) was further used as a mask, and disposed so that thepolarizing direction was perpendicular to the diffraction gratingpattern and that the incidence angle was 45° with respect to thesubstrate. Then, as energy beams, ultraviolet rays having a wavelengthof 365 nm (i rays) (at 3 mJ/cm² after passing through the mask) wasradiated at 500 W by using an extra-high pressure mercury lamp for 40seconds (FIG. 32 (d)), so as to further react and crosslink theremaining unreacted energy beam sensitive groups.

[0315] In this state, a liquid crystal cell was assembled, and nematicliquid crystal was injected. When the orientation state was observed, itwas confirmed that the liquid crystal was aligned in the direction ofthe grating pattern, and that the pre-tilt angle was about 20°. It wasalso confirmed in this second irradiation that it was possible tocontrol the pre-tilt angle of the injected liquid crystal by changingthe irradiation angle. The alignment films produced by theabove-described two processes without no further treatment were usableas alignment films, but when a heat treatment was performed at about150° C., the alignment property of the alignment films deteriorated.

[0316] Therefore, in order to further improve the thermal stability ofthe alignment film, the alignment film was heated at 180° C. for 10minutes, so as to open and crosslink the thermoreactive glycidyl groups(i.e., thermosetting groups). In this state, a liquid crystal cell wasassembled, and nematic liquid crystal was injected. When the orientationstate was observed, it was confirmed that the liquid crystal was alignedin a direction perpendicular to the grating pattern, and that thepre-tilt angle was about 7°. Furthermore, the thermal stability of thealignment film was improved to 170° C.

[0317] The reaction by exposure of the photosensitive and thermosettingfilm and the reaction by heating are both crosslinking reactions, asshown by (formula 36) below.

[0318] Furthermore, a substance containing no hydrocarbon group (—CH₃)was synthesized and the same experiment was performed. As a result, thealignment controllability, especially the control stability of thepre-tilt angle, of the liquid crystal was worse than one containing—CH₃.

[0319] As described above, for the film in this example, the energy beamsensitive group was a photosensitive group, and light was radiatedthrough a mask to react the photosensitive groups in the film so as notonly to crosslink the principal chains but also to fix and align sidechain groups. Furthermore, since the film was sensitive to i rays (seeFIG. 33), it was possible to use an ordinary exposure apparatus, therebysimplifying the production process of the liquid crystal alignment film.

[0320] Furthermore, when the resin film is exposed to light through apolarizing film and a diffraction grating as a mask, a liquid crystalalignment film having striped convexities and concavities was producedon the surface of the film easily.

[0321] At this time, by changing light exposure, or by performingexposure obliquely through a polarizing film and a diffraction grating,or by performing exposure obliquely through a polarizing film and thenperforming exposure through a diffraction grating, or by performingexposure through a diffraction grating and then performing exposureobliquely through a polarizing film, the pre-tilt angle of interposedliquid crystal was controlled. Thus, a liquid crystal alignment filmhaving a stable alignment property was produced. In order to stabilizethe pre-tilt angle by one exposure, it was important to expose thephotosensitive film to light to an extent that predetermined convexitiesand concavities are generated on the surface thereof.

[0322] Furthermore, when heat is applied so as to react thermoreactivegroups before or after radiating energy beams so as to react andcrosslink the energy beam sensitive groups, the heat resistance of thealignment of the alignment film was improved. Electron beams, X rays, orultraviolet rays are usable as the energy beams, but ultraviolet raysprovided a higher practicability in an actual production process.

[0323] As described above, a resin film transparent in a visible lightrange and having energy beam sensitive groups and thermoreactive groupswas formed directly on electrodes or indirectly via an arbitrary thinfilm, and a rubbing free liquid crystal alignment film formed of a filmobtained by at least reacting the energy beam sensitive groups wasproduced by a remarkably simple method.

EXAMPLE 20

[0324] Next, a liquid crystal display device using the above-describedalignment film and a production method thereof will be described indetail with reference to FIG. 34.

[0325] First, a resin transparent in a visible light range and havingenergy beam sensitive groups and thermoreactive groups as represented by(formula 1) was diluted in cyclohexanone to 0.5% so as to prepare asensitizing solution beforehand. Then, as shown in FIG. 34, a firstsubstrate 153 includes first electrode arrays 151 mounted in a matrixand transistor arrays 152 for driving the electrodes. A second substrate156 includes color filter arrays 154 and second electrodes 155 opposedto the first electrode arrays. The sensitizing solution was applied ontothe first substrate and the second substrate by a dipping method, so asto form a photosensitive and thermosetting resin film.

[0326] Thereafter, the film was heated at 100° C. for 10 minutes so asto remove the solvent to some extent. Then, using a diffraction gratingof 1000 slits per mm as a mask, and disposing the grating parallel tothe electrode pattern, ultraviolet rays having a wavelength of 365 nm (irays) (at 28 mJ/cm² after passing through the mask) was radiated at 500W by using an extra-high pressure mercury lamp from the verticaldirection for 5 seconds, so as to react and crosslink benzalacetophenonegroups, which are the energy beam sensitive groups. Then, a liquidcrystal alignment film 157 provided with concavities and convexities ofabout 30 to 40 nm was produced.

[0327] Next, the first and the second substrates 153 and 156 werepositioned so that they were opposed to each other, and fixed withspacers 158 and an adhesive 159 with about a 5 micron gap. Thereafter,the liquid crystal 160 was injected between the first and the secondsubstrates, and polarizing plates 161 and 162 were provided. Thus, adisplay device was completed. Such a device was able to display imagesin the direction shown by arrow A by being entirely irradiated withbacklight 163 and by driving each transistor with video signals.

[0328] Industrial Applicability

[0329] As described above, the first liquid crystal alignment film ofthe present invention has an effect of producing a uniform and thinalignment film in a desired pattern efficiently without performingrubbing.

[0330] Furthermore, in producing the liquid crystal alignment film, byrepeating the process using the method of chemically adsorbing a silanesurfactant to the surfaces of the electrodes along the exposure patternto form one layer of a monomolecular film several times, a liquidcrystal alignment film having a multi-domain where a plurality oforientations are present in each pixel can be produced easily.

[0331] Furthermore, the use of such a liquid crystal alignment filmeliminates a chance of generating defects as generated in a conventionalrubbing process, and provides a liquid crystal display apparatus havinga remarkably high yield, a low cost and high reliability and beingcapable of displaying at a wide viewing angle.

[0332] Furthermore, a specific liquid crystal, for example nematicliquid crystal or ferroelectric liquid crystal, can be incorporated intothe bonds in the alignment film formed by adsorption, so that itprovides an excellent alignment controllability.

[0333] As described above, the second liquid crystal alignment film ofthe present invention has an effect of efficiently and rationallyproducing an alignment film having a function of controlling thepre-tilt angle of liquid crystal and aligning liquid crystal in anarbitrary direction by controlling the critical surface energy of thealignment film without using rubbing as conventionally performed.

[0334] Furthermore, the method for producing the liquid crystalalignment film of the present invention efficiently provides analignment film having an excellent adhesion strength where the moleculesconstituting the film are aligned uniformly in a specific direction andbonded to the surface of the substrate at one end.

[0335] Furthermore, at the time of producing the liquid crystalalignment film, if the process of exposure through a patterned maskdisposed on a polarizing plate is performed a plurality of times, aplurality of portions each having a different patterned orientation canbe formed on one face of the alignment film. This makes it possible toeasily produce a liquid crystal display apparatus having a multi-domainwhere a plurality of orientations are present in each pixel, which wasdifficult with conventional rubbing.

[0336] Furthermore, the use of such a liquid crystal alignment filmeliminates a chance of generating defects as generated in a conventionalrubbing process, and provides a liquid crystal display apparatus havinga remarkably high yield, a low cost and high reliability and beingcapable of displaying at a wide viewing angle.

[0337] Furthermore, a specific liquid crystal, for example nematicliquid crystal or ferroelectric liquid crystal, can be incorporated intothe bonds in the alignment film formed by adsorption, so that itprovides an excellent alignment controllability.

[0338] As described above, the third liquid crystal alignment film ofthe present invention has an effect of efficiently producing a uniformand thin alignment film having a function of controlling the pre-tiltangle of liquid crystal and aligning liquid crystal in an arbitrarydirection without using rubbing as conventionally performed.

[0339] Furthermore, at the time of producing the liquid crystalalignment film, if the process of exposure through a patterned maskdisposed on a polarizing plate is performed a plurality of times, aplurality of portions, each having a different patterned orientation,can be formed on one face of the alignment film. This makes it possibleto efficiently produce a liquid crystal display apparatus having amulti-domain where a plurality of orientations are present in eachpixel, which was difficult with conventional rubbing.

[0340] Furthermore, the use of such a liquid crystal alignment filmeliminates a chance of generating defects as generated in a conventionalrubbing process, and provides a desired pre-tilt angle and a liquidcrystal display apparatus having a remarkably high yield, a low cost andhigh reliability and being capable of displaying at a wide viewingangle.

[0341] Furthermore, liquid crystal having a specific surface energy, forexample nematic liquid crystal or ferroelectric liquid crystal, can beincorporated into the bonds in the alignment film formed by adsorption.Therefore, it is possible to efficiently produce an alignment filmhaving not only the controllability of the orientation and the tiltangle, but also an excellent alignment regulation force.

[0342] As described above, the fourth liquid crystal alignment film ofthe present invention has an effect of producing a uniform and thinalignment film in a short time efficiently without performingconventional rubbing.

[0343] Furthermore, the use of such a liquid crystal alignment filmprovides a liquid crystal display apparatus having a remarkably highyield, a low cost and high reliability without performing conventionalrubbing.

1. A liquid crystal alignment film, which is a film wherein asilane-based surfactant having a linear carbon chain and Si ischemically adsorbed via an energy beam sensitive resin film forgenerating functional groups containing active hydrogen by energy beamirradiation formed on a predetermined surface of a substrate, where thelinear carbon chains are aligned in a specific direction.
 2. The liquidcrystal alignment film according to claim 1, wherein the film formed ofthe surfactant is fixed to the energy beam sensitive resin film viacovalent bonds on the surface of the substrate in a striped pattern. 3.The liquid crystal alignment film according to claim 2, wherein thefixed film formed of the surfactant is fixed to the energy beamsensitive resin film via a film having siloxane bonds.
 4. The liquidcrystal alignment film according to any one of claims 1 to 3, whereinthe silane-based surfactant is a chlorosilane-based surfactantcontaining a linear hydrocarbon group and a chlorosilyl group.
 5. Theliquid crystal alignment film according to claim 4, wherein a part ofhydrogen of the linear hydrocarbon group of the chlorosilane-basedsurfactant is substituted with at least a fluorine atom.
 6. The liquidcrystal alignment film according to claim 4 or 5, wherein a plurality oftypes of chlorosilane-based surfactants, each having a differentmolecular length, are mixed and used as the chlorosilane-basedsurfactant containing a linear hydrocarbon group and a chlorosilylgroup.
 7. A liquid crystal alignment film, which is a monomolecular filmformed on a surface of a substrate provided with desired electrodes,wherein the molecules constituting the film have a desired tilt and arebonded and fixed to the surface of the substrate at one end while beingaligned uniformly in a specific direction.
 8. The liquid crystalalignment film according to claim 7, wherein the desired tilt of themolecules is defined by fixing the molecules constituting the film tothe substrate by covalent bonds, washing the molecules with an organicsolvent, and tilting the substrate in a desired direction so as to drainoff the solvent.
 9. The liquid crystal alignment film according to claim7 or 8, wherein the molecules constituting the film contain carbonchains or siloxane bond chains.
 10. The liquid crystal alignment filmaccording to claim 9, wherein a carbon of a part of the carbon chain hasan optical activity.
 11. The liquid crystal alignment film according toany one of claims 7 to 10, wherein the molecules constituting the filmhave Si at both ends.
 12. The liquid crystal alignment film according toany one of claims 7 to 11, wherein the molecules constituting the filmare formed by mixing a plurality of types of chemisorption moleculeshaving different molecular lengths, and the fixed film has concavitiesand convexities on a molecular length level.
 13. A liquid crystalalignment film, which is a monomolecular film formed on a surface of asubstrate provided with desired electrodes, wherein the moleculesconstituting the film have carbon chains or siloxane bond chains, and atleast a part of the carbon chain or the siloxane bond chain contains atleast a functional group for controlling a surface energy of the film.14. The liquid crystal alignment film according to claim 13, wherein aplurality of types of silane-based surfactants, each having a differentcritical surface energy, are mixed and used as the moleculesconstituting the film, and the fixed film is controlled so as to have adesired critical surface energy.
 15. The liquid crystal alignment filmaccording to claim 13 or 14, wherein the functional group forcontrolling the surface energy is at least one organic group selectedfrom the group consisting of a carbon trifluoride group (—CF₃), a methylgroup (—CH₃), a vinyl group (—CH═CH₃), an allyl group (—CH═CH—), anacetylene group (triple bonds of carbon-carbon), a phenyl group (—C₆H₅),an aryl group (—C₆H₄—), a halogen atom, an alkoxy group (—OR; Rrepresents an alkyl group), a cyano group (—CN), an amino group (—NH₂),a hydroxyl group (—OH), a carbonyl group (═CO), an ester group (—COO—)and a carboxyl group (—COOH).
 16. The liquid crystal alignment filmaccording to any one of claims 13 to 15, wherein the moleculesconstituting the film contain Si at the terminals.
 17. The liquidcrystal alignment film according to any one of claims 13 to 16, whereinthe critical surface energy of the film is controlled to be a desiredvalue between 15 mN/m to 56 mN/m.
 18. A liquid crystal alignment film,wherein a resin film transparent in visible light range and havingenergy beam sensitive groups and thermoreactive groups is formeddirectly on electrodes or indirectly via an arbitrary thin film, and atleast the energy beam sensitive groups are reacted and crosslinked. 19.The liquid crystal alignment film according to claim 18, wherein theenergy beam sensitive groups and the thermoreactive groups areintroduced as side chain groups in the resin film. 20 The liquid crystalalignment film according to claim 18, wherein the energy beam sensitivegroups, the thermoreactive groups and hydrocarbon groups are introducedas side chain groups in the resin film.
 21. The liquid crystal alignmentfilm according to claim 18, wherein the surface of the resin film hasstriped concavities and convexities.
 22. The liquid crystal alignmentfilm according to any one of claim 18 to 21, wherein the thermoreactivegroups are reacted and crosslinked.
 23. The liquid crystal alignmentfilm according to claim 18, wherein a substance represented by(formula 1) is used as the resin film.


24. A method for producing a liquid crystal alignment film comprisingthe steps of applying and forming an energy beam sensitive resin filmfor generating functional groups containing active hydrogen by energybeams directly or indirectly via an arbitrary thin film on apredetermined surface of a substrate provided with electrodes,irradiating the surface of the resin film with energy beams in anarbitrary pattern, contacting the irradiated resin film with achemisorption solution containing a silane-based surfactant havinglinear carbon chains and Si groups, washing the substrate with a solventincapable of dissolving the resin film, thereby forming one layer of amonomolecular film formed of the surfactant selectively in theirradiated portion, and aligning and fixing the linear carbon chains inthe surfactant molecules.
 25. The method for producing a liquid crystalalignment film according to claim 24, wherein the energy beams are atleast one light selected from the group consisting of electron beams, Xrays or light with a wavelength of 100 nm to 1 μm.
 26. The method forproducing a liquid crystal alignment film according to claim 25, whereinthe chemisorption solution contains at least a chlorosilane-basedsurfactant comprising a linear carbon chain and a chlorosilyl group anda solvent that causes no damage to the energy beam sensitive resin film.27. The method for producing a liquid crystal alignment film accordingto claim 25 or 26, wherein the energy beams are at least one lightselected from the group consisting of ultraviolet rays, visible rays andinfrared rays, and the energy beam sensitive resin film is aphotosensitive resin film.
 28. The method for producing a liquid crystalalignment film according to claim 27, wherein the photosensitive resinfilm is a polymer film or a monomer film containing at least one organicgroup selected from the group consisting of a group represented by(formula 2), a group represented by (formula 3) and a group representedby (formula 4).


29. The method for producing a liquid crystal alignment film accordingto any one of claims 24 to 28, wherein a solvent including a carbonfluoride group is used as a nonaqueous solvent.
 30. A method forproducing a monomolecular liquid crystal alignment film comprising thesteps of contacting a substrate provided with electrodes with achemisorption solution so as to cause a chemical reaction betweenmolecules of a surfactant in the adsorption solution and a surface ofthe substrate, thereby bonding and fixing the surfactant molecules tothe surface of the substrate at one end, washing the substrate with anorganic solvent, and tilting the substrate in a desired direction so asto drain off the solvent, thereby aligning the fixed molecules in thedirection in which the solvent was drained off.
 31. The method forproducing a monomolecular liquid crystal alignment film according toclaim 30 further comprising the step of exposing the substrate to lightpolarized in a desired direction via a polarizing plate after the stepof aligning the molecules, so as to align the orientations of thesurfactant molecules uniformly in a specific direction at a desiredtilt.
 32. The method for producing a monomolecular liquid crystalalignment film according to claim 30 or 31, wherein a silane-basedsurfactant containing linear hydrocarbon groups or siloxane bond chainsand chlorosilyl groups, alkoxysilyl groups or isocyanate silyl groups isused as the surfactant.
 33. The method for producing a monomolecularliquid crystal alignment film according to claim 32, wherein a pluralityof types of silane-based surfactants, each having a different molecularlength, are mixed and used as the silane-based surfactant containinglinear hydrocarbon groups or siloxane bond chains and chlorosilylgroups, alkoxysilyl groups or isocyanate silyl groups.
 34. The methodfor producing a monomolecular liquid crystal alignment film according toclaim 32 or 33, wherein a carbon of a part of the hydrocarbon group hasan optical activity.
 35. The method for producing a monomolecular liquidcrystal alignment film according to any one of claims 32 to 34, whereinthe hydrocarbon group or the siloxane bond chain contains a halogen atomor a methyl group (—CH₃), a phenyl group (—C₆H₅), a cyano group (—CN), ahydroxyl group (—OH), a carboxyl group (—COOH), an amino group (—NH₂),or a carbon trifluoride group (—CF₃) at the terminal.
 36. The method forproducing a monomolecular liquid crystal alignment film according toclaim 31, wherein light that is used for exposure is light having atleast one wavelength selected from the group consisting of 436 nm, 405nm, 365 nm, 254 nm and 248 nm.
 37. The method for producing amonomolecular liquid crystal alignment film according to any one ofclaims 32 to 36, wherein a silane-based surfactant containing linearhydrocarbon groups or siloxane bond chains and chlorosilyl groups orisocyanate silyl groups is used as the surfactant, and a nonaqueousorganic solvent containing no water is used as the washing organicsolvent.
 38. The method for producing a monomolecular liquid crystalalignment film according to claim 37, wherein a solvent containing analkyl group, a carbon fluoride group or a carbon chloride group or asiloxane group is used as the nonaqueous organic solvent.
 39. The methodfor producing a monomolecular liquid crystal alignment film according toany one of claims 30 to 38, wherein a film containing a large number ofSiO groups is formed before the step of fixing the surfactant moleculesat one end, and then a monomolecular film is formed via this film.
 40. Amethod for producing a monomolecular liquid crystal alignment filmcomprising the steps of contacting a substrate provided with electrodeswith a chemisorption solution produced by using a silane-basedsurfactant containing carbon chains or siloxane bond chains, at least apart of the carbon chain or the siloxane bond chain containing at leastone functional group for controlling a surface energy of a formed film,thereby causing a chemical reaction between the surfactant molecules inthe adsorption solution and the surface of the substrate so as to bondand fix the surfactant molecules to the surface of the substrate at oneend.
 41. The method for producing a monomolecular liquid crystalalignment film according to claim 40, wherein a silane-based surfactantcontaining linear carbon chains or siloxane bond chains and chlorosilylgroups, alkoxysilyl groups or isocyanate silyl groups is used as thesurfactant.
 42. The method for producing a monomolecular liquid crystalalignment film according to claim 40 or 41, wherein a plurality of typesof silicon-based surfactants having cifferent critical surface energiesare mixed and used as the surfactant.
 43. The method for producing amonomolecular liquid crystal alignment film according to any one ofclaim 40 or 42, wherein a terminal or a part of the carbon chain or thesiloxane bond chain comprises at least one organic group selected fromthe group consisting of a carbon trifluoride group (—CF₃), a methylgroup (—CH₃), a vinyl group (—CH═CH₂), an allyl group (—CH═CH—), anacetylene group (triple bonds of carbon-carbon), a phenyl group (—C₆H₅),an aryl group (—C₆H₄—), a halogen atom, an alkoxy group (—OR; Rrepresents an alkyl group), a cyano group (—CN), an amino group (—NH₂),a hydroxyl group (—OH), a carbonyl group (═CO), an ester group (—COO—)and a carboxyl group (—COOH).
 44. The method for producing amonomolecular liquid crystal alignment film according to any one ofclaim 40 or 43, further comprising the steps of washing the substratewith an organic solvent after the step of bonding and fixing thesurfactant molecules to the surface of the substrate at one end, andtilting the substrate in a desired direction so as to drain off thesolvent, thereby aligning the fixed molecules in the direction in whichthe solvent was drained off.
 45. The method for producing amonomolecular liquid crystal alignment film according to claim 44further comprising the step of exposing the substrate to light through apolarizing film after the step of aligning the molecules, so as torealign the molecules in a desired direction.
 46. The method forproducing a monomolecular liquid crystal alignment film according toclaim 44 to 45, wherein a silane-based surfactant containing linearcarbon chains or siloxane bond chains and chlorosilyl groups orisocyanate silane groups is used as the surfactant, and a nonaqueousorganic solvent containing no water is used as the washing organicsolvent.
 47. The method for producing a monomolecular liquid crystalalignment film according to claim 46, wherein a solvent containing analkyl group, a carbon fluoride group or a carbon chloride group or asiloxane group is used as the nonaqueous organic solvent.
 48. The methodfor producing a monomolecular liquid crystal alignment film according toany one of claims 40 to 47, further comprising the step of forming afilm containing a large number of SiO groups before the step of fixingthe surfactant molecules at one end, and then forming a monomolecularfilm via this film.
 49. A method for producing a liquid crystalalignment film comprising the steps of applying and forming a resin filmtransparent in a visible light range and having energy beam sensitivegroups and thermoreactive groups on a predetermined surface of asubstrate provided with electrodes directly or indirectly via anarbitrary thin film, and at least irradiating the resin film with energybeams through an arbitrary mask so as to react and crosslink the energybeam sensitive groups.
 50. The method for producing a liquid crystalalignment film according to claim 49, wherein the step of reacting andcrosslinking the thermoreactive groups by heating is added before orafter the step of reacting and crosslinking the energy beam sensitivegroups.
 51. The method for producing a liquid crystal alignment filmaccording to claim 49 or 50, wherein the energy beam sensitive groupsare photosensitive groups, and the resin film is irradiated withultraviolet rays through a mask so that the photosensitive groups in theresin film react not only to crosslink between principal chains but alsoto align and fix side chain groups.
 52. The method for producing aliquid crystal alignment film according to any one of claims 49 to 51,wherein a polarizing film or a diffraction grating is used as the maskfor exposure.
 53. The method for producing a liquid crystal alignmentfilm according to any one of claims 49 to 52, wherein in the step ofexposure, the resin film is exposed to light to an extent thatconcavities and convexities are generated on the surface thereof.
 54. Aliquid crystal display apparatus comprising a pair of substrates,electrodes and alignment films, the electrodes being formed on thesurfaces of the substrates, the alignment films being formed thereon,liquid crystal being interposed between the counter electrodes on thetwo substrates via the alignment films, wherein at least one alignmentfilm is a film in which a silane-based surfactant having a linear carbonchain is chemically adsorbed via an energy beam sensitive film forgenerating a functional group containing active hydrogen by irradiationof energy beams, and the linear carbon chains are aligned in a specificdirection.
 55. A liquid crystal display apparatus, wherein a film isformed as an alignment film for liquid crystal directly on a surfaceprovided with electrodes on at least one substrate of two substratesprovided with counter electrodes or indirectly via another film, thefilm being a monomolecular film formed of a silane-based surfactanthaving linear carbon chains or siloxane bond chains, moleculesconstituting the film having a desired tilt and being bonded and fixedto the surface of the substrate at one end while being aligned uniformlyin a specific direction, liquid crystal being interposed between thecounter electrodes on the two substrates via the alignment film.
 56. Theliquid crystal display apparatus according to claim 55, wherein saidfilm is formed on each of the surfaces of the two substrates providedwith the counter electrodes as the alignment film.
 57. The liquidcrystal display apparatus according to claim 55 or 56, wherein the filmon the surface of the substrate comprises a plurality of patternedsections each having a different alignment direction.
 58. The liquidcrystal display apparatus according to claim 55, wherein the counterelectrodes are formed on a surface of one substrate.
 59. A liquidcrystal display apparatus, wherein a film is formed as an alignment filmfor liquid crystal directly on a surface provided with electrodes of atleast one substrate of two substrates provided with counter electrodesor indirectly via another film, the film being constituted by moleculescontaining carbon chains or siloxane bond chains, a part of the carbonchain or the siloxane bond chain containing at least one functionalgroup for controlling a surface energy of the film, liquid crystal beinginterposed between the counter electrodes on the two substrates via thealignment film.
 60. The liquid crystal display apparatus according toclaim 59, wherein said film is formed on each of the surfaces of the twosubstrates provided with the counter electrodes as the alignment film.61. The liquid crystal display apparatus according to claim 59 or 60,wherein the film on the surface of the substrate comprises a pluralityof patterned sections, each having a different alignment direction. 62.The liquid crystal display apparatus according to claim 59, wherein thecounter electrodes are formed on a surface of one substrate.
 63. Aliquid crystal display apparatus, wherein a resin film transparent in avisible light range and having energy beam sensitive groups andthermoreactive groups is formed directly on electrodes or indirectlythrough an arbitrary thin film, and at least the energy beam sensitivegroups are reacted and crosslinked, the thus obtained liquid crystalalignment film being formed on electrodes on at least one substrates oftwo substrates provided with counter electrodes, liquid crystal beinginterposed between the counter electrodes on the two substrates via theresin film.
 64. A method for producing a liquid crystal displayapparatus comprising the steps of applying and forming an energy beamsensitive resin film for generating functional groups containing activehydrogen by energy beams directly or indirectly via an arbitrary thinfilm on a first substrate including first electrode arrays arranged in amatrix beforehand, irradiating the surface of the resin film with energybeams in an arbitrary pattern, contacting the substrate with theirradiated resin film with a chemisorption solution containing asilane-based surfactant having linear carbon chains and Si, washing thesubstrate with a solvent incapable of dissolving the resin film so as toform one layer of a monomolecular film formed of the surfactantselectively in the irradiated portion, and aligning and mixing thelinear carbon chains, attaching the first substrate including the firstelectrode arrays to a second substrate including second electrodes orelectrode arrays so that the respective electrodes are opposed with apredetermined gap, and injecting predetermined liquid crystal betweenthe first substrate and the second substrate.
 65. A method for producinga liquid crystal display apparatus comprising the steps of contacting afirst substrate including first electrode arrays arranged in a matrixbeforehand with a chemisorption solution directly or after forming anarbitrary thin film so as to cause a chemical reaction between thesurfactant molecules in the adsorption solution and the surface of thesubstrate, thereby bonding and fixing the surfactant molecules to thesurface of the substrate at one end, washing the substrate with anorganic solvent, tilting the substrate in a desired direction so as todrain off the solvent, thereby aligning the fixed molecules in thedirection in which the solvent is drained off, exposing the substrate tolight polarized in a desired direction through a polarizing plate so asto align the orientations of the surfactant molecules uniformly in aspecific direction at a desired tilt, attaching the first substrateincluding the first electrode arrays to a second substrate or a secondsubstrate including second electrodes or electrode arrays so that thefaces provided with the electrodes are facing inward with apredetermined gap, and injecting predetermined liquid crystal betweenthe first substrate and the second substrate.
 66. The method forproducing a liquid crystal display apparatus according to claim 65,wherein in the step of exposing the substrate to light polarized in adesired direction through a polarizing plate so as to align theorientations of the bonded surfactant molecules uniformly in a specificdirection at a desired tilt, the step of exposure with a patterned maskdisposed on the polarizing plate is performed several times so as toform a plurality of patterned sections each having a different alignmentdirection on one face of the alignment film.
 67. A method for producinga liquid crystal display apparatus comprising the steps of contacting afirst substrate including first electrode arrays arranged in a matrixbeforehand with a chemisorption solution directly or after forming anarbitrary thin film, the chemisorption solution being produced by usinga silane-based surfactant containing carbon chains or siloxane bondchains, at least a part of the carbon chain or the siloxane bond chaincontaining at least one functional group for controlling a surfaceenergy of a formed film, so as to cause a chemical reaction between thesurfactant molecules in the adsorption solution and the surface of thesubstrate, thereby bonding and fixing the surfactant molecules to thesurface of the substrate at one end, washing the substrate with anorganic solvent, tilting the substrate in a desired direction so as todrain off the solvent, thereby aligning the fixed molecules in thedirection in which the solvent is drained off, attaching the firstsubstrate including the first electrode arrays to a second substrate ora second substrate including second electrodes or electrode arrays sothat the faces provided with the electrodes are facing inward with apredetermined gap, and injecting predetermined liquid crystal betweenthe first substrate and the second substrate.
 68. The method forproducing a liquid crystal display apparatus according to claim 67,further comprising the step of exposing the substrate to light polarizedin a desired direction through a polarizing plate so as to align theorientations of the surfactant molecules uniformly in a specificdirection at a desired tilt after the step of aligning the fixedmolecules.
 69. The method for producing a liquid crystal displayapparatus according to claim 68, wherein in the step of exposing thesubstrate to light polarized in a desired direction through a polarizingplate so as to align the orientations of the bonded surfactant moleculesuniformly in a specific direction at a desired tilt, the step ofexposure with a patterned mask disposed on the polarizing plate isperformed several times, thereby forming a plurality of patternedsections each having a different alignment direction on one face of thealignment film.
 70. A method for producing a liquid crystal displayapparatus comprising the steps of applying and forming a resin filmtransparent in a visible light range and having energy beam sensitivegroups and thermoreactive groups directly or indirectly via an arbitrarythin film on a first substrate including first electrode arrays arrangedin a matrix, at least irradiating the resin film with energy beamsthrough an arbitrary mask so as to react and crosslink the energy beamsensitive groups, attaching the first substrate including the firstelectrode arrays to a second substrate including second electrodes orelectrode arrays opposed to the first electrode arrays so that therespective faces provided with the electrodes are opposed to each other,and injecting predetermined liquid crystal between the first substrateand the second substrate.